Nothing Special   »   [go: up one dir, main page]

EP0964744B1 - Method for producing phthalic anhydride; shell catalyst containing titanium-vanadium-cesium - Google Patents

Method for producing phthalic anhydride; shell catalyst containing titanium-vanadium-cesium Download PDF

Info

Publication number
EP0964744B1
EP0964744B1 EP98912298A EP98912298A EP0964744B1 EP 0964744 B1 EP0964744 B1 EP 0964744B1 EP 98912298 A EP98912298 A EP 98912298A EP 98912298 A EP98912298 A EP 98912298A EP 0964744 B1 EP0964744 B1 EP 0964744B1
Authority
EP
European Patent Office
Prior art keywords
weight
catalyst
calculated
catalytically active
xylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98912298A
Other languages
German (de)
French (fr)
Other versions
EP0964744A1 (en
Inventor
Gerhard Hefele
Otto Kratzer
Walter Scheidmeir
Bernhard Ulrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0964744A1 publication Critical patent/EP0964744A1/en
Application granted granted Critical
Publication of EP0964744B1 publication Critical patent/EP0964744B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen

Definitions

  • the present invention relates to a method for manufacturing of phthalic anhydride by catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas and a coated catalyst from an inert, non-porous carrier material the catalytic one containing titanium dioxide and vanadium pentoxide active mass is applied in layers, and a catalyst therefor.
  • the PSA catalysts consist of generally from an inert carrier material on which a thin Layer of the catalytically active mass applied in a bowl shape is why these catalysts are commonly called shell catalysts be designated.
  • the composition of the catalytically active composition plays an important role in the catalytic properties of these PSA catalysts.
  • Practically all PSA catalysts used today contain the components titanium dioxide in their catalytically active composition, generally in the anatase modification, and vanadium pentoxide. Since PSA catalysts, whose catalytically active mass consists solely of these basic components, in terms of conversion, yield and selectivity as a result of side reactions, such as the formation of phthalide of the formula
  • DE-A 24 36 009 and DE-A 24 21 406 describe shell catalysts used on a steatite support for the production of PSA, which in their catalytically active mass 60 to 99 wt .-% titanium dioxide in the anatase modification, 1 to 40 wt .-% vanadium pentoxide and based on the titanium dioxide 0.15 to 1.5 wt .-% of rubidium and / or Contains cesium.
  • DE-A 25 10 994 relates to vanadium- and titanium-containing supported catalysts of a certain external shape, the catalytically active mass of 70 to 99% by weight of titanium dioxide in the anatase modification and a specific internal surface area of 5 to 20 m 2 / g, 1 to 30 wt .-% vanadium pentoxide and up to a proportion of 5 wt .-% also other substances, such as the oxides of the elements cesium, rubidium, thallium, phosphorus or antimony. No information is given on the exact content of these other substances, in particular their quantitative relationships with one another. Steatite (magnesium silicate) is used as the carrier material.
  • DE-A 25 47 624 describes catalysts for the production of PSA which contain 60 to 99% by weight of titanium dioxide (anatase), 1 to 40% by weight of vanadium pentoxide and 0.1 to 10% by weight of rubidium and antimony contain an atomic ratio Rb: Sb of 1: 2.5 to 1:30 in their catalytically active mass.
  • the anatase used can then have an inner surface area of 5 to 50, preferably 5 to 20 m 2 / g; according to the exemplary embodiment, anatase with an inner surface area of 11 m 2 / g is used.
  • EP-A 21 325 relates to coated catalysts for the production of PSA which contain 60 to 99% by weight of anatase, 1 to 40% by weight of vanadium pentoxide and, based on the total amount of -TiO 2 and V 2 O 5 , in the catalytically active composition contain up to 2% by weight of phosphorus and up to 1.5% by weight of rubidium and / or cesium, the catalytically active composition being applied to the support in two layers, the inner layer of which is 0.2 to 2% by weight. % Phosphorus, but no rubidium or cesium and their outer layer contains 0 to 0.2% by weight phosphorus and 0.02 to 1.5% by weight rubidium and / or cesium.
  • the catalytically active composition of these catalysts can also contain small amounts, for example up to 10% by weight, of an oxide of the metals niobium, tin, silicon, antimony, hafnium, molybdenum or tungsten.
  • the titanium dioxide used to produce these catalysts has an internal surface area of 5 to 30 m 2 / g. Steatite is used as the carrier material.
  • EP-A 286 448 relates to a process for the production of PSA the two types of catalysts in a combined catalyst bed are used, both of which have similar levels of titanium dioxide and contain vanadium pentoxide and essentially differ in that the one additional catalyst 2 to 5% by weight of a cesium compound, especially cesium sulfate, however no phosphorus, tin, antimony, bismuth, tungsten or Contains molybdenum compounds and the second catalyst additionally 0.1 to 3% by weight of a phosphorus, tin, antimony, bismuth, Tungsten or molybdenum compound, but practically no alkali metal contains.
  • EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 29 48 163 and DE-A 30 45 624 all relate to catalysts for the production of PSA, which is preferably made of a porous support material Silicon carbide and a catalytically active mass, which in addition Titanium dioxide and vanadium pentoxide are a variety of other catalytic effective elements such as phosphorus, alkali metals, antimony (in EP-A 522 871 pentavalent antimony), niobium and / or silver, contains, are composed.
  • the present invention was therefore based on the object Processes for making PPE that are free of the The above-mentioned disadvantages and is a suitable catalyst for this to provide.
  • the method according to the invention should be used especially in long-term operation with high o-xylene loads consistently good yields of PSA with a high degree of purity deliver and so a chemical processing of the raw PPE for Removal disadvantageous, but practically hardly separable by distillation Eliminate by-products such as phthalide.
  • a process for the preparation of phthalic anhydride by the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas over a coated catalyst from an inert, non-porous support material, on which a titanium dioxide and vanadium pentoxide containing catalytically active composition is applied in layers which is characterized in that a catalyst whose catalytically active composition is 3 to 6 wt .-% of vanadium pentoxide, calculated as V 2 O 5 , 0.3 to 0.5 wt .-% of a cesium compound, calculated as Cs, and the rest 100% by weight of titanium dioxide in the anatase modification, in the presence or absence of a shell catalyst different from this for the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / Naphthalene mixtures, used and
  • a process for the preparation of phthalic anhydride by the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas over a coated catalyst made of an inert, non-porous support material onto a titanium dioxide and vanadium pentoxide containing catalytically active composition is applied in a layered form, which is characterized in that a coated catalyst is used in a first reaction zone located towards the gas inlet into the reactor, the catalytically active composition of which is 3 to 6% by weight of vanadium pentoxide, calculated as V 2 O.
  • a coated catalyst the catalytically active mass of 1 to 10 wt .-% from vanadium pentoxide, calculated as V 2 O 5 , from 0 to 10% by weight from antimony oxide, calculated as Sb 2 O 3 , from 0.01 to 0.3% by weight from a cesium and / or rubidium compound as Cs or Rb, 0.01 to 0.3% by weight of a phosphorus compound, calculated as P, and the rest 100% by weight of titanium dioxide in the anatase modification.
  • a catalyst consisting of a thin layer of catalytically active components, which is applied in the form of a shell on a non-porous support material, has a catalytically active mass of 3 to 6% by weight of vanadium pentoxide, calculated as V 2 O 5 , of 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder consisting of 100% by weight of titanium dioxide in the anatase modification.
  • the catalyst according to the invention can be used alone or preferably in a combined fill with a second or more of them various catalysts in the process according to the invention be used.
  • the catalyst according to the invention is preferred in a combined bed with a second catalyst used, in particular with a second catalyst of the previous described composition.
  • the method according to the invention is thus preferably used a combined catalyst bed, i.e. the two catalysts used according to the invention are in the individual reaction tubes of the PSA reactor in a fixed bed arranged one above the other so that the first catalyst for gas entry of the educt gas flow is located in the reactor, whereas the second catalyst for the gas outlet of the reaction gases is located out of the reactor. Since the implementation of the aromatic Hydrocarbon takes place in the catalyst bed, becomes the section filled with the relevant catalysts of the reaction tube or tubes also as a reaction zone and with the first and second catalyst filled section of the Reaction zone also referred to as the first or second reaction zone.
  • the proportion of the first reaction zone to the volume of the above Reaction zone between 25 and 75 vol .-%, preferably are between 50 and 70 vol .-%.
  • a coated catalyst is advantageously used according to the invention, on the inert, non-porous support material which is heat-resistant under the conditions of the PSA production, the catalytically active composition is applied in a shell-shaped layer, this catalytically active composition, based on the weight of this, catalytically active mass in the finished catalyst, generally 3 to 6% by weight, preferably 3 to 5% by weight and particularly preferably 3.5 to 4.5% by weight of vanadium pentoxide, calculated as V 2 O 5 , and in general 0.3 to 0.5 wt .-%, preferably 0.35 to 0.45 wt .-% of a cesium compound, calculated as Cs, and the rest to 100 wt .-% of the catalytically active mass of titanium dioxide in its anatase -Modification exists. Since it is not known in which form or compounds the cesium is present in the finished catalyst, the content of cesium compounds is calculated as Cs.
  • the catalyst can be heat-resistant support material sintered or melted silicates, e.g. steatite (Magnesium silicate), porcelain, clay, non-porous silicon carbide, Contain rutile or quartz, the carrier material is preferred in the catalyst used according to the invention steatite.
  • the Backing material can be coated with the catalytically active Mass e.g. in the form of balls, cylinders, spirals or rings are used, preferably a carrier in the form of rings, as described in DE-A 25 10 994 used.
  • the catalyst takes the catalytically active mass, based on the Total weight of the catalyst, generally 8 to 12 wt .-%, preferably from 9 to 11 wt .-% and particularly preferably from 9.5 to 10.5% by weight.
  • finished catalyst is in this application the one with the catalytically active Mass coated, if necessary for the transfer of precursor compounds of the catalytically active components in this catalytically active components and for the removal of organic aids heat-treated, ready-to-use for catalyst production Understood catalyst.
  • titanium dioxide is used in the anatase modification, which generally has a BET surface area of 13 to 28 m 2 / g, particularly preferably 19 to 21 m 2 / g and a grain size of generally 0.12 to 1 ⁇ , preferably from 0.4 to 0.8 ⁇ .
  • the catalyst to be used according to the invention in the second reaction zone is different from the catalyst in the first reaction zone. It is particularly preferred to use a catalyst in the second reaction zone which, in its catalytically active composition, based on the total weight of the catalytically active composition in the finished catalyst, generally 1 to 10% by weight, preferably 2 to 9% by weight and particularly preferably 3 to 8% by weight of vanadium pentoxide, calculated as V 2 O 5 , generally 0 to 10% by weight, preferably 0 to 5% by weight and particularly preferably 0 to 4% by weight of antimony oxide, calculated as Sb 2 O 3 , generally 0.01 to 0.3% by weight, preferably 0.05 to 0.3% by weight and particularly preferably 0.1 to 0.25% by weight of a cesium and / or Rubidium compound, calculated as Cs or Rb, and generally 0.01 to Q.3% by weight, preferably 0.05 to 0.3% by weight and particularly preferably 0.1 to 0.25% by weight a phosphorus compound, calculated as P, contains.
  • Catalysts with a different composition from the above Composition are used, for example with commercially available catalysts or catalysts such as them e.g. in DE-A 25 46 268, EP-A 286 448, DE-A 25 47 624, DE-A 29 48 163, EP-A 163 231, DE-A 28 30 765, DE-A 17 69 998, EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 30 45 624 or DE-A 40 13 051 are described.
  • this can contain antimony or be antimony-free.
  • the antimony oxide can be present in these catalysts, for example, as Sb 2 O 3 , Sb 2 O 4 or Sb 2 O 5 , Sb 2 O 3 is preferably used for the preparation of the catalyst.
  • the information on the composition of the in the second reaction zone preferably used catalyst give the composition the catalytically active mass, i.e. the element components, that were actively used to manufacture them. Possibly in the starting materials for the production of the catalytically active Mass contained, technically unavoidable impurities not taken into account in this information, as this is not for everyone Component and were not analyzed in every trial.
  • Catalysts which can be used advantageously can be conventional per se Way by applying the catalytically active composition or of precursor compounds of the catalytically active mass contained catalytically active components on the carrier, for example as described in DE-A 25 10 994, by spraying one of the components of the catalytically active composition or their mash containing precursor compounds on e.g. preheated to 100 to 450 ° C, for example in a Coating drum.
  • the catalytically active mass can also be different by spraying, e.g. by applying a the catalytically active Components or their precursors and aids for pasty mass containing catalyst preparation the carrier, e.g.
  • a coating drum or by application one of the catalytically active components and / or their Containing precursor compounds, e.g. by spray or Freeze drying of prefabricated powder on the carrier material, e.g. in a coating drum, during the coating process a small amount of a solvent to mediate the Adhesion of the powder on the preheated carrier in the coating device is sprayed, subsequent drying and optionally calcination at temperatures up to 450 ° C, preferably up to 400 ° C, are applied to the carrier material.
  • the catalytically active components of the catalyst or their precursor compounds are, for example, in the form of their oxides, salts, their nitrates, C 1 - to C 10 -carboxylates, carbonates, bicarbonates, sulfates, hydrogen sulfates, halides or Phosphates or as complex compounds, for example as oxalate or acetylacetone complexes and, if appropriate, auxiliaries used for catalyst preparation are dissolved in a solvent or, if these substances are not individually soluble, suspended.
  • Both water and organic liquids or mixtures of water with these liquids can be used as solvents or suspending agents. Water or water in a mixture with organic liquids is preferably used, the mixing ratio water / organic liquid generally not being critical, but preference being given to using solvent mixtures which contain 50 or more percent by weight of water.
  • Organic liquids which are preferably water-soluble solvents, such as C 1 to C 4 alcohols, water-soluble ethers, for example tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, water-soluble amides, for example formamide, pyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide or water-soluble sulfoxides, for example Dimethyl sulfoxide used.
  • water-soluble solvents such as C 1 to C 4 alcohols, water-soluble ethers, for example tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, water-soluble amides, for example formamide, pyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide or water-soluble sulfoxides, for example Dimethyl sulfoxide used.
  • the mash can be used as an aid for catalyst production or the pasty mass of binders, pore formers and / or temporary Activity dampers are added.
  • binder means substances the adhesion of the individual particles of the catalytically active Mass or their precursors to each other and / or Improve permanently or temporarily on the carrier material.
  • polyols such as ethylene glycol, Propylene glycol, butylene glycols or glycerin or amides, such as Formamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dibutylformamide, Acetamide, pyrrolidone or N-methylpyrrolidone used become.
  • pore formers which in the active mass by a change in volume, for example by evaporation or decomposition during the heat treatment Generation of the catalytically active metal oxides from them Precursor compounds in the manufacture of the coated catalyst, the formation of a compared to an active mass, in the production of which no pore former was added, changed Cause pore structure.
  • pore formers can Processes according to the invention, for example polyols, such as glycerol or polymers such as cellulose, methyl cellulose, cellulose acetate or starch, or acids such as oxalic acid, tartaric acid or lactic acid, or also amines, such as melamine, or amides, such as urea, be used.
  • the type and amount of tools to be added generally depends on the chemical composition the catalytically active mass of the shell catalyst in question and the raw materials used and will expediently for the catalytically active to be generated in each case Mass of certain chemical composition in a preliminary test optimized.
  • temporary activity suppressants are used above specified binders or pore formers or beyond understood all other excipients for a limited period of time decrease in activity and / or decrease the hot spot temperature and thus the start of the Reactor or the load increase until its full load operation facilitate without the mean catalytic activity or Reduce selectivity.
  • the catalysts thus produced are preferably used for gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures used to phthalic anhydride.
  • the catalysts to be used according to the invention are filled into the reaction tubes, which are then advantageously thermostatted to the reaction temperature from the outside, for example by means of a salt bath.
  • the reaction gas at temperatures of generally 300 to 450 ° C, preferably from 320 to 420 ° C and particularly preferably from 340 to 400 ° C and at an excess pressure of generally 0.1 to 2.5 bar , preferably from 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h -1 passed .
  • the reaction gas fed to the catalyst is generally obtained by mixing a gas containing molecular oxygen, preferably air, which, in addition to oxygen, may also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized generated, the molecular oxygen-containing gas generally 1 to 100 vol%, preferably 2 to 50 vol% and particularly preferably 10 to 30 vol% oxygen, 0 to 30 vol%, preferably 0 to 10 vol% water vapor and 0 to 50 vol%, preferably 0 to 1 vol% carbon dioxide, the rest nitrogen.
  • a gas containing molecular oxygen preferably air
  • suitable reaction moderators and / or diluents such as steam, carbon dioxide and / or nitrogen
  • the molecular oxygen-containing gas is generally with 40 g to 140 g per Nm 3 of gas, preferably with 60 to 120 g per Nm 3 of gas and particularly preferably with 80 to 115 g per Nm 3 of the aromatic gas to be oxidized Charged with hydrocarbon.
  • the gas phase oxidation can advantageously be carried out in such a way that that you have two or more zones, preferably two zones in the reaction tube located catalyst bed on different Reaction temperatures thermostated, for example Reactors with separate salt baths, e.g. in DE-A 22 01 528 or DE-A 28 30 765 are used can be.
  • the reaction zone located towards the gas inlet of the reactant gas which, as already mentioned, generally 25 to 75% by volume of the total Volume of the catalyst, to a temperature of 1 to 20 ° C, preferably 1 to 10 ° C and in particular 2 to 8 ° C higher reaction temperature than the reaction zone towards the gas outlet be thermostatted.
  • the gas phase oxidation even without division into temperature zones in both reaction zones be carried out at the same reaction temperature.
  • the reaction is through the temperature setting of the salt bath so that the largest in the first zone Part of the aromatic hydrocarbon contained in the feed gas is implemented at maximum yield.
  • the aromatic Almost hydrocarbon in the first reaction zone fully implemented at maximum yield.
  • the process according to the invention avoids the disadvantages of the PSA processes and catalysts of the prior art, even when the feed gas stream is loaded with o-xylene and / or naphthalene of 80 g / Nm 3 gas and higher.
  • the BET surface area was determined by the method of Brunauer et al, J. Am. Chem. Soc. 60 , 309 (1938).
  • the catalytically active composition applied in this way contained 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3.2% by weight. % Antimony (calculated as Sb 2 O 3 ), 0.1% by weight cesium (calculated as Cs) and 88.75% by weight titanium dioxide.
  • 700 g steatite rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated in a coating drum to 160 ° C and with a suspension of 400 g anatase with a BET surface area of 21 m 2 / g, 30.7 g of vanadyl oxalate, 3.33 g of ammonium hydrogen phosphate, 2.60 g of cesium sulfate, 618 g of water and 128 g of formamide were sprayed until the weight of the layer applied corresponded to 10.5% of the total weight of the finished catalyst.
  • the catalytically active composition applied in this way contained 4.0% by weight of vanadium (calculated as V 2 O 5 ), 0.2% by weight of cesium (calculated as Cs), 0.2% by weight. % Phosphorus (calculated as P) and 95.4% by weight titanium dioxide.
  • Catalyst I was used in the first reaction zone and catalyst II in the second reaction zone, the catalytically active composition of which had the following composition in% by weight, based on the weight of the catalytically active composition in the finished catalyst:
  • Catalyst I Catalyst II V 2 O 5 4.0 7.5 Sb 2 O 3 - 3.2 Cs 0.4 0.1 Phosphorus (P) - 0.15 rest anatase anatase
  • the fill level of the Catalyst II was 130 cm, that of Catalyst I 160 cm. in the The upper part was the reaction tube at the gas inlet in one length of 50 cm free of catalyst.
  • the reaction tube was equipped with a liquid heat transfer medium (salt bath) thermostatted the heat of reaction was also removed.
  • the catalyst carrier consisted of cylindrical rings in dimensions 6 mm (height), 8 mm (width) and 5 mm (clear width).
  • the reaction tube was flowed through with 4 m 3 of air per hour from top to bottom, the o-xylene loading being 95 g / m 3 of air.
  • the purity of the o-xylene was 98.2%.
  • the hot spot temperature in the catalyst bed reached 430 to 440 ° C.
  • the hot spot was about 40 to 60 cm deep in the first reaction zone.
  • the reaction gas emerging from the reaction tube consisted of its organic components to 95.8 wt .-% from phthalic anhydride.
  • the main by-products were maleic anhydride (3.2% by weight), benzoic acid (0.51% by weight), phthalide (0.07% by weight) and citraconic anhydride (0.34% by weight).
  • the amount of PSA formed was 435 g / h, corresponding to a PSA yield of 83.5 mol% based on 100% o-xylene.
  • the end crude PSA separated from the reaction gas could be in a 2-stage Vacuum distillation without problems and without pretreatment Process pure PSA of GC purity 99.9%.
  • the melt color number was 5 to 10 (APHA), the heat color number (90 min at 250 ° C) 10 to 20 (APHA).
  • Catalyst I was used in the first reaction zone and catalyst III in the second reaction zone, the catalytically active composition of which had the following composition in% by weight, based on the weight of the catalytically active composition in the finished catalyst:
  • Catalyst I Catalyst III V 2 O 5 4.0 4.0 Cs 0.4 0.2 Phosphorus (P) - 0.2 rest anatase anatase
  • the filling height of the catalyst III was 130 cm, that of the catalyst I 170 cm.
  • the upper part of the reaction tube was empty at a length of 40 cm at the gas inlet.
  • the reaction tube was filled with a liquid heat transfer medium (Salt bath) thermostatted, via which the heat of reaction is also dissipated has been.
  • Salt bath liquid heat transfer medium
  • the catalyst carrier consisted of cylindrical rings in dimensions 6.5 mm (height), 7 mm (width) and 4 mm (clear width).
  • the reaction tube from Example 1 was flowed through with 4 m 3 of air per hour from top to bottom.
  • the o-xylene loading in the air was 85 g / m 3 .
  • the purity of the o-xylene was 98.2%.
  • the hot spot temperature reached 435 to 445 ° C.
  • the hot spot was about 60 to 70 cm deep in the first reaction zone.
  • the reaction gas emerging from the reaction tube consisted of its organic components to 95.9 wt .-% from phthalic anhydride.
  • the main by-products were maleic anhydride (2.87% by weight), benzoic acid (0.49% by weight), phthalide (0.18% by weight) and citraconic anhydride (0.35% by weight).
  • the substances that are problematic for environmental protection are o-xylene and The concentrations of benzene were comparable to those in Example 1 described before. A depletion from the exhaust gas was also here not mandatory.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

In a process for preparing phthalic anhydride by catalytic gas-phase oxidation of o-xylene or naphthalene or o-xylene/naphthalene mixtures with a gas comprising molecular oxygen over a coated catalyst comprising an inert, nonporous support material on which a catalytically active composition comprising titanium dioxide and vanadium pentoxide is applied in layer form, a catalyst whose catalytically active composition comprises from 3 to 6% by weight of vanadium pentoxide, calculated as V2O5, from 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder to 100% by weight of titanium dioxide in the anatase modification is used in the presence or absence of a coated catalyst, differing therefrom, for the catalytic gas-phase oxidation of o-xylene or naphthalene or o-xylene/naphthalene mixtures and, in the presence of such a second catalyst, the latter is used in a combined bed with the catalyst of the above composition in the reactor.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Phthalsäureanhydrid durch die katalytische Gasphasenoxidation von o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen mit einem molekularen Sauerstoff enthaltenden Gas und einem Schalenkatalysator aus einem inerten, nicht-porösen Trägermaterial auf das eine Titandioxid und Vanadiumpentoxid enthaltende katalytisch aktive Masse schichtförmig aufgebracht ist, sowie einen Katalysator hierfür.The present invention relates to a method for manufacturing of phthalic anhydride by catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas and a coated catalyst from an inert, non-porous carrier material the catalytic one containing titanium dioxide and vanadium pentoxide active mass is applied in layers, and a catalyst therefor.

Für die Herstellung von PSA aus o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen durch deren Oxidation mit molekularen Sauerstoff enthaltenden Gasen in der Gasphase an einem Festbettkatalysator wurden im Stand der Technik eine Vielzahl von katalysatoren vorgeschlagen. Die PSA-Katalysatoren bestehen im allgemeinen aus einem inerten Trägermaterial, auf das eine dünne Schicht der katalytisch aktiven Masse schalenförmig aufgetragen ist, weshalb diese Katalysatoren gemeinhin auch als Schalenkatalysatoren bezeichnet werden.For the production of PSA from o-xylene or naphthalene or o-xylene / naphthalene mixtures through their oxidation with molecular Gases containing oxygen in the gas phase on a fixed bed catalyst a variety of catalysts proposed. The PSA catalysts consist of generally from an inert carrier material on which a thin Layer of the catalytically active mass applied in a bowl shape is why these catalysts are commonly called shell catalysts be designated.

Für die katalytischen Eigenschaften dieser PSA-Katalysatoren spielt die Zusammensetzung der katalytisch aktiven Masse eine maßgebliche Rolle. Praktisch alle heutzutage genutzten PSA-Katalysatoren enthalten in ihrer katalytisch aktiven Masse die Komponenten Titandioxid, im allgemeinen in der Anatas-Modifikation, und Vanadiumpentoxid. Da PSA-Katalysatoren, deren katalytisch aktive Masse allein aus diesen Grundkomponenten besteht, hinsichtlich Umsatz, Ausbeute und Selektivität infolge von Nebenreaktionen, wie der Bildung von Phthalid der Formel

Figure 00010001
The composition of the catalytically active composition plays an important role in the catalytic properties of these PSA catalysts. Practically all PSA catalysts used today contain the components titanium dioxide in their catalytically active composition, generally in the anatase modification, and vanadium pentoxide. Since PSA catalysts, whose catalytically active mass consists solely of these basic components, in terms of conversion, yield and selectivity as a result of side reactions, such as the formation of phthalide of the formula
Figure 00010001

Maleinsäureanhydrid, Benzoesäure und Citraconsäureanhydrid der Formel

Figure 00020001
oder der Totalverbrennung, wirtschaftlich unbefriedigende Ergebnisse zeitigen und auch hinsichtlich Langzeitaktivität und -selektivität nicht zufriedenstellen können, gingen die Bestrebungen im Stand der Technik dahin, diese Katalysatoren durch Dotierung der katalytisch aktiven Masse mit den verschiedensten Zusatzstoffen und immer mehr Zusatzstoffen hinsichtlich ihrer Aktivität, Selektivität, Ausbeute und der Qualität des damit produzierten PSA-Produktes zu verbessern, d.h. es wurden mit der Zeit immer kompliziertere Katalysatorrezepte zur Lösung dieser Probleme entwickelt. Solche Zusatzstoffe sind z.B. Antimon, Bor, Cäsium, Calcium, Kobalt, Eisen, Kalium, Lithium, Molybdän, Natrium, Niob, Phosphor, Rubidium, Silber, Thallium, Wismut, Wolfram und Zinn.Maleic anhydride, benzoic acid and citraconic anhydride of the formula
Figure 00020001
or total combustion, produce economically unsatisfactory results and cannot satisfy long-term activity and selectivity either, efforts in the prior art have been directed towards doping the catalytically active composition with a wide variety of additives and more and more additives with regard to their activity, selectivity, To improve the yield and the quality of the PSA product produced with it, ie over time, increasingly complex catalyst recipes have been developed to solve these problems. Such additives are, for example, antimony, boron, cesium, calcium, cobalt, iron, potassium, lithium, molybdenum, sodium, niobium, phosphorus, rubidium, silver, thallium, bismuth, tungsten and tin.

In DE-A 24 36 009 und DE-A 24 21 406 werden Schalenkatalysatoren auf einem Steatitträger zur Herstellung von PSA verwendet, die in ihrer katalytisch aktiven Masse 60 bis 99 Gew.-% Titandioxid in der Anatas-Modifikation, 1 bis 40 Gew.-% Vanadiumpentoxid und bezogen auf das Titandioxid 0,15 bis 1,5 Gew.-% an Rubidium und/oder Cäsium enthalten.DE-A 24 36 009 and DE-A 24 21 406 describe shell catalysts used on a steatite support for the production of PSA, which in their catalytically active mass 60 to 99 wt .-% titanium dioxide in the anatase modification, 1 to 40 wt .-% vanadium pentoxide and based on the titanium dioxide 0.15 to 1.5 wt .-% of rubidium and / or Contains cesium.

DE-A 25 10 994 betrifft Vanadium- und Titan-haltige Trägerkatalysatoren einer bestimmten äußeren Form, die in ihrer katalytisch aktiven Masse 70 bis 99 Gew.-% Titandioxid in der Anatas-Modifikation und einer spezifischen inneren Oberfläche von 5 bis 20 m2/g, 1 bis 30 Gew.-% Vanadiumpentoxid und bis zu einem Anteil von 5 Gew.-% auch noch andere Stoffe, wie die Oxide der Elemente Cäsium, Rubidium, Thallium, Phosphor oder Antimon enthalten kann. Über den genauen Gehalt an diesen anderen Stoffen, insbesondere deren Mengenverhältnisse untereinander, werden keine Angaben gemacht. Als Trägermaterial wird Steatit (Magnesiumsilikat) verwendet.DE-A 25 10 994 relates to vanadium- and titanium-containing supported catalysts of a certain external shape, the catalytically active mass of 70 to 99% by weight of titanium dioxide in the anatase modification and a specific internal surface area of 5 to 20 m 2 / g, 1 to 30 wt .-% vanadium pentoxide and up to a proportion of 5 wt .-% also other substances, such as the oxides of the elements cesium, rubidium, thallium, phosphorus or antimony. No information is given on the exact content of these other substances, in particular their quantitative relationships with one another. Steatite (magnesium silicate) is used as the carrier material.

In DE-A 25 47 624 werden Katalysatoren zur Herstellung von PSA beschrieben, die 60 bis 99 Gew.-% Titandioxid (Anatas), 1 bis 40 Gew.-% Vanadiumpentoxid und 0,1 bis 10 Gew.-% Rubidium und Antimon in einem Atomverhältnis Rb:Sb von 1:2,5 bis 1:30 in ihrer katalytisch aktiven Masse enthalten. Der verwendete Anatas kann danach eine innere Oberfläche von 5 bis 50, vorzugsweise 5 bis 20 m2/g haben, gemäß Ausführungsbeispiel wird Anatas mit einer inneren Oberfläche von 11 m2/g verwendet.DE-A 25 47 624 describes catalysts for the production of PSA which contain 60 to 99% by weight of titanium dioxide (anatase), 1 to 40% by weight of vanadium pentoxide and 0.1 to 10% by weight of rubidium and antimony contain an atomic ratio Rb: Sb of 1: 2.5 to 1:30 in their catalytically active mass. The anatase used can then have an inner surface area of 5 to 50, preferably 5 to 20 m 2 / g; according to the exemplary embodiment, anatase with an inner surface area of 11 m 2 / g is used.

EP-A 21 325 betrifft Schalenkatalysatoren zur Herstellung von PSA, die in der katalytisch aktiven Masse 60 bis 99 Gew.-% Anatas, 1 bis 40 Gew.-% Vanadiumpentoxid und, bezogen auf die Gesamtmenge an -TiO2 und V2O5, bis zu 2 Gew.-% Phosphor und bis zu 1,5 Gew.-% Rubidium und/oder Cäsium enthalten, wobei die katalytisch aktive Masse in zwei Schichten auf den Träger aufgetragen ist, deren innere Schicht 0,2 bis 2 Gew.-% Phosphor, aber kein Rubidium oder Cäsium und deren äußere Schicht 0 bis 0,2 Gew.-% Phosphor und 0,02 bis 1,5 Gew.-% Rubidium und/oder Cäsium enthält. Die katalytisch aktive Masse dieser Katalysatoren kann außer den genannten Bestandteilen noch kleine Mengen, z.B. bis zu 10 Gew.-% eines Oxids der Metalle Niob, Zinn, Silicium, Antimon, Hafnium, Molybdän oder Wolfram enthalten. Das zur Herstellung dieser Katalysatoren verwendete Titandioxid hat eine innere Oberfläche von 5 bis 30 m2/g. Als Trägermaterial wird Steatit verwendet.EP-A 21 325 relates to coated catalysts for the production of PSA which contain 60 to 99% by weight of anatase, 1 to 40% by weight of vanadium pentoxide and, based on the total amount of -TiO 2 and V 2 O 5 , in the catalytically active composition contain up to 2% by weight of phosphorus and up to 1.5% by weight of rubidium and / or cesium, the catalytically active composition being applied to the support in two layers, the inner layer of which is 0.2 to 2% by weight. % Phosphorus, but no rubidium or cesium and their outer layer contains 0 to 0.2% by weight phosphorus and 0.02 to 1.5% by weight rubidium and / or cesium. In addition to the constituents mentioned, the catalytically active composition of these catalysts can also contain small amounts, for example up to 10% by weight, of an oxide of the metals niobium, tin, silicon, antimony, hafnium, molybdenum or tungsten. The titanium dioxide used to produce these catalysts has an internal surface area of 5 to 30 m 2 / g. Steatite is used as the carrier material.

EP-A 286 448 betrifft ein Verfahren zur Herstellung von PSA, bei dem zweierlei Katalysatoren in einer kombinierten Katalysatorschüttung eingesetzt werden, die beide ähnliche Gehalte an Titandioxid und Vanadiumpentoxid enthalten und sich im wesentlichen dadurch unterscheiden, daß der eine Katalysator zusätzlich 2 bis 5 Gew.-% einer Cäsiumverbindung, insbesondere Cäsiumsulfat, jedoch keine Phosphor-, Zinn-, Antimon-, Wismut-, Wolfram- oder Molybdänverbindungen enthält und der zweite Katalysator zusätzlich 0,1 bis 3 Gew.-% einer Phosphor-, Zinn-, Antimon-, Wismut-, Wolfram- oder Molybdänverbindung, jedoch praktisch kein Alkalimetall enthält.EP-A 286 448 relates to a process for the production of PSA the two types of catalysts in a combined catalyst bed are used, both of which have similar levels of titanium dioxide and contain vanadium pentoxide and essentially differ in that the one additional catalyst 2 to 5% by weight of a cesium compound, especially cesium sulfate, however no phosphorus, tin, antimony, bismuth, tungsten or Contains molybdenum compounds and the second catalyst additionally 0.1 to 3% by weight of a phosphorus, tin, antimony, bismuth, Tungsten or molybdenum compound, but practically no alkali metal contains.

EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 29 48 163 und DE-A 30 45 624 betreffen allesamt Katalysatoren zur Herstellung von PSA, die aus einem porösen Trägermaterial, vorzugsweise Siliciumcarbid und einer katalytisch aktiven Masse, die neben Titandioxid udn Vanadiumpentoxid eine Vielzahl weiterer Katalytisch wirksamer Elemente, wie Phosphor, Alkalimetalle, Antimon (in EP-A 522 871 fünfwertiges Antimon), Niob und/oder Silber, enthält, zusammengesetzt sind.EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 29 48 163 and DE-A 30 45 624 all relate to catalysts for the production of PSA, which is preferably made of a porous support material Silicon carbide and a catalytically active mass, which in addition Titanium dioxide and vanadium pentoxide are a variety of other catalytic effective elements such as phosphorus, alkali metals, antimony (in EP-A 522 871 pentavalent antimony), niobium and / or silver, contains, are composed.

Trotz Fortschritten in der Katalysator-Entwicklung sind die heute bekannten und verfügbaren Katalysatoren und Katalysatorsysteme für die Herstellung von Phthalsäureanhydrid weiterhin mit einer Reihe von Nachteilen behaftet. Die mit einem frischen Katalysator erzielbare anfängliche PSA-Ausbeute liegt bei etwa 80 mol-%, aber bereits im ersten Betriebsjahr ist ein deutlicher Ausbeuteabfall hinzunehmen. Aus Qualitätsgründen muß das zunächst als Rohware anfallende Phthalsäureanhydrid einer chemischen Behandlung unterworfen werden, ehe es anschließend destillativ zu Reinprodukt im heute geforderten Qualitätsstandard aufgearbeitet werden kann. Wegen ihrer großen Empfindlichkeit gegenüber Temperatur-, Druckund Beladungsschwankungen ist für die sichere Nutzung dieser Katalysatoren im Großbetrieb ein hoher Überwachungs- und Kontrollaufwand erforderlich. Ein weiterer Nachteil ergibt sich für diese Katalysatoren dadurch, daß aufgrund ihres unvollständigen o-Xylol-Umsatzes und dem Entstehen von unter- bzw. überoxidierten Nebenprodukten Geruchsprobleme sowie o-Xylol- und Benzolemissionen entstehen, die aus Umweltgründen eine aufwendige Abgasverbrennung erforderlich machen.Despite advances in catalyst development, they are today known and available catalysts and catalyst systems for the production of phthalic anhydride continue with a A number of disadvantages. The one with a fresh catalyst achievable initial PSA yield is around 80 mol%, however there is already a significant drop in yield in the first year of operation to accept. For quality reasons, this must first be raw resulting phthalic anhydride is subjected to a chemical treatment be before it is distilled to pure product in the quality standard required today can be worked up. Because of their great sensitivity to temperature, pressure and Load fluctuations is essential for the safe use of these Catalysts in large operations require a high level of monitoring and control required. Another disadvantage arises for these catalysts in that because of their incomplete o-xylene conversion and the formation of under- or over-oxidized By-products odor problems as well as o-xylene and benzene emissions arise that for environmental reasons a complex exhaust gas combustion make necessary.

Diese Nachteile verstärken sich bei hohen Beladungen des Eduktgasstroms mit o -Xylol und/oder Naphthalin, insbesondere bei Beladungen von 80 g o-Xylol je Nm3 Gas und mehr.These disadvantages are exacerbated when the feed gas stream is loaded with o -xylene and / or naphthalene, in particular with loads of 80 g of o-xylene per Nm 3 of gas or more.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zur Herstellung von PSA zu finden, das frei von den obengenannten Nachteilen ist und hierfür einen geeigneten Katalysator zur Verfügung zu stellen. Das erfindungsgemäße Verfahren sollte insbesondere im Langzeitbetrieb mit hohen o-Xylolbeladungen dauerhaft gute Ausbeuten von PSA mit einem hohen Reinheitsgrad liefern und so eine chemische Aufarbeitung des rohen PSA zur Abtrennung nachteiliger, aber destillativ praktisch kaum abtrennbarer Nebenprodukte, wie Phthalid, überflüssig machen.The present invention was therefore based on the object Processes for making PPE that are free of the The above-mentioned disadvantages and is a suitable catalyst for this to provide. The method according to the invention should be used especially in long-term operation with high o-xylene loads consistently good yields of PSA with a high degree of purity deliver and so a chemical processing of the raw PPE for Removal disadvantageous, but practically hardly separable by distillation Eliminate by-products such as phthalide.

Dementsprechend wurde ein Verfahren zur Herstellung von Phthalsäureanhydrid durch die katalytische Gasphasenoxidation von o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen mit einem molekularen Sauerstoff enthaltenden Gas an einem Schalenkatalysator aus einem inerten, nicht-porösen Trägermaterial, auf das eine Titandioxid und Vanadiumpentoxid enthaltende katalytisch aktive Masse schichtförmig aufgebracht ist, gefunden, das dadurch gekennzeichnet ist, daß man einen Katalysator dessen katalytisch aktive Masse zu 3 bis 6 Gew.-% aus Vanadiumpentoxid, berechnet als V2O5, zu 0,3 bis 0,5 Gew.-% aus einer Cäsiumverbindung, berechnet als Cs, und der Rest zu 100 Gew.-% aus Titandioxid in der Anatasmodifikation besteht, in An- oder Abwesenheit eines von diesem verschiedenen Schalenkatalysator zur katalytischen Gasphasenoxidation von o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen, verwendet und bei Anwesenheit eines solchen zweiten Katalysators, diesen in einer kombinierten Schüttung mit dem Katalysator obenstehender Zusammensetzung im Reaktor einsetzt. Accordingly, a process for the preparation of phthalic anhydride by the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas over a coated catalyst from an inert, non-porous support material, on which a titanium dioxide and vanadium pentoxide containing catalytically active composition is applied in layers, which is characterized in that a catalyst whose catalytically active composition is 3 to 6 wt .-% of vanadium pentoxide, calculated as V 2 O 5 , 0.3 to 0.5 wt .-% of a cesium compound, calculated as Cs, and the rest 100% by weight of titanium dioxide in the anatase modification, in the presence or absence of a shell catalyst different from this for the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / Naphthalene mixtures, used and in the presence of such a second catalyst, this in a combination first bed with the catalyst of the above composition in the reactor.

Insbesondere wurde ein Verfahren zur Herstellung von Phthalsäureanhydrid durch die katalytische Gasphasenoxidation von o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen mit einem molekularen Sauerstoff enthaltenden Gas an einem Schalenkatalysator aus einem inerten, nicht-porösen Trägermaterial auf das eine Titandioxid und Vanadiumpentoxid enthaltende katalytisch aktive Masse schichtförmig aufgebracht ist, gefunden, das dadurch gekennzeichnet ist, daß man in einer ersten zum Gaseintritt in den Reaktor hin gelegenen Reaktionszone einen Schalenkatalysator einsetzt, dessen katalytisch aktive Masse 3 bis 6 Gew.-% aus Vanadiumpentoxid, berechnet als V2O5, zu 0,3 bis 0,5 Gew.-% aus einer Cäsiumverbindung, berechnet als Cs und der Rest zu 100 Gew.-% aus Titandioxid in der Anatas-Modifikation besteht und einer zweiten zum Austritt der Reaktionsgase aus dem Reaktor hin gelegenen Reaktionszone einen Schalenkatalysator verwendet, dessen katalytisch aktive Masse zu 1 bis 10 Gew.-% aus Vanadiumpentoxid, berechnet als V2O5, zu 0 bis 10 Gew.-% aus Antimonoxid, berechnet als Sb2O3, zu 0,01 bis 0,3 Gew.-% aus einer Cäsium- und/oder Rubidiumverbindung, berechnet als Cs bzw. Rb, zu 0,01 bis 0,3 Gew.-% aus einer Phosphorverbindung, berechnet als P, und im Rest zu 100 Gew.-% aus Titandioxid in der Anatas-Modifikation besteht.In particular, a process for the preparation of phthalic anhydride by the catalytic gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures with a molecular oxygen-containing gas over a coated catalyst made of an inert, non-porous support material onto a titanium dioxide and vanadium pentoxide containing catalytically active composition is applied in a layered form, which is characterized in that a coated catalyst is used in a first reaction zone located towards the gas inlet into the reactor, the catalytically active composition of which is 3 to 6% by weight of vanadium pentoxide, calculated as V 2 O. 5 , 0.3 to 0.5 wt .-% of a cesium compound, calculated as Cs and the rest of 100 wt .-% of titanium dioxide in the anatase modification and a second to the exit of the reaction gases from the reactor Reaction zone uses a coated catalyst, the catalytically active mass of 1 to 10 wt .-% from vanadium pentoxide, calculated as V 2 O 5 , from 0 to 10% by weight from antimony oxide, calculated as Sb 2 O 3 , from 0.01 to 0.3% by weight from a cesium and / or rubidium compound as Cs or Rb, 0.01 to 0.3% by weight of a phosphorus compound, calculated as P, and the rest 100% by weight of titanium dioxide in the anatase modification.

Desweiteren wurde ein Katalysator aus einer dünnen Schicht katalytisch aktiver Komponenten, die auf einem nicht-porösen Trägermaterial schalenförmig aufgebracht ist, dessen katalytisch aktive Masse zu 3 bis 6 Gew.-% aus Vanadiumpentoxid, berechnet als V2O5, zu 0,3 bis 0,5 Gew.-% aus einer Cäsiumverbindung, berechnet als Cs, und der Rest zu 100 Gew.-% aus Titandioxid in der Anatas-Modifikation besteht, gefunden.Furthermore, a catalyst consisting of a thin layer of catalytically active components, which is applied in the form of a shell on a non-porous support material, has a catalytically active mass of 3 to 6% by weight of vanadium pentoxide, calculated as V 2 O 5 , of 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder consisting of 100% by weight of titanium dioxide in the anatase modification.

Der erfindungsgemäße Katalysator kann allein oder vorzugsweise in einer kombinierten Schüttung mit einem zweiten oder mehreren davon verschiedenen Katalysatoren im erfindungsgemäßen Verfahren eingesetzt werden. Bevorzugt wird der erfindungsgemäße Katalysator in einer kombinierten Schüttung mit einem zweiten Katalysator eingesetzt, insbesondere mit einem zweiten Katalysator der zuvor beschriebenen Zusammensetzung.The catalyst according to the invention can be used alone or preferably in a combined fill with a second or more of them various catalysts in the process according to the invention be used. The catalyst according to the invention is preferred in a combined bed with a second catalyst used, in particular with a second catalyst of the previous described composition.

Das erfindungsgemäße Verfahren wird somit vorzugsweise unter Anwendung einer kombinierten Katalysatorschüttung ausgeführt, d.h. die beiden erfindungsgemäß verwendeten Katalysatoren werden in den einzelnen Reaktionsrohren des PSA-Reaktors in einem Festbett übereinander angeordnet, so daß der erste Katalysator zum Gaseintritt des Eduktgasstroms in den Reaktor hin gelegen ist, wohingegen der zweite Katalysator zum Gasaustritt der Reaktionsgase aus dem Reaktor hin gelegen ist. Da die Umsetzung des aromatischen Kohlenwasserstoffs in der Katalysatorschüttung stattfindet, wird der mit den betreffenden Katalysatoren befüllte Abschnitt des oder der Reaktionsrohre auch als Reaktionszone und der mit dem ersten bzw. zweiten Katalysator befüllte Abschnitt der Reaktionszone auch als erste bzw. zweite Reaktionszone bezeichnet. Je nach Art der erfindungsgemäß verwendeten PSA-Katalysatoren kann der Anteil der ersten Reaktionszone am Volumen der genannten Reaktionszone zwischen 25 und 75 Vol.-%, vorzugsweise zwischen 50 und 70 Vol.-% liegen.The method according to the invention is thus preferably used a combined catalyst bed, i.e. the two catalysts used according to the invention are in the individual reaction tubes of the PSA reactor in a fixed bed arranged one above the other so that the first catalyst for gas entry of the educt gas flow is located in the reactor, whereas the second catalyst for the gas outlet of the reaction gases is located out of the reactor. Since the implementation of the aromatic Hydrocarbon takes place in the catalyst bed, becomes the section filled with the relevant catalysts of the reaction tube or tubes also as a reaction zone and with the first and second catalyst filled section of the Reaction zone also referred to as the first or second reaction zone. Depending on the type of PSA catalysts used according to the invention can the proportion of the first reaction zone to the volume of the above Reaction zone between 25 and 75 vol .-%, preferably are between 50 and 70 vol .-%.

In der ersten Reaktionszone wird erfindungsgemäß vorteilhaft ein Schalenkatalysator verwendet, auf dessen inertes, nicht-poröses unter den Bedingungen der PSA-Herstellung hitzebeständiges Trägermaterial die katalytisch aktive Masse in einer schalenförmigen Schicht aufgebracht ist, wobei diese katalytisch aktive Masse, bezogen auf das Gewicht dieser katalytisch aktiven Masse im fertigen Katalysator, im allgemeinen 3 bis 6 Gew.-%, vorzugsweise 3 bis 5 Gew.-% und besonders bevorzugt 3,5 bis 4,5 Gew.-% Vanadiumpentoxid, berechnet als V2O5, sowie im allgemeinen 0,3 bis 0,5 Gew.-%, bevorzugt 0,35 bis 0,45 Gew.-% einer Cäsiumverbindung, berechnet als Cs, enthält und der Rest zu 100 Gew.-% der katalytisch aktiven Masse aus Titandioxid in dessen Anatas-Modifikation besteht. Da nicht bekannt ist, in Form welcher Verbindung oder Verbindungen das Cäsium im fertigen Katalysator vorliegt, wird der Gehalt an Cäsiumverbindungen als Cs berechnet.In the first reaction zone, a coated catalyst is advantageously used according to the invention, on the inert, non-porous support material which is heat-resistant under the conditions of the PSA production, the catalytically active composition is applied in a shell-shaped layer, this catalytically active composition, based on the weight of this, catalytically active mass in the finished catalyst, generally 3 to 6% by weight, preferably 3 to 5% by weight and particularly preferably 3.5 to 4.5% by weight of vanadium pentoxide, calculated as V 2 O 5 , and in general 0.3 to 0.5 wt .-%, preferably 0.35 to 0.45 wt .-% of a cesium compound, calculated as Cs, and the rest to 100 wt .-% of the catalytically active mass of titanium dioxide in its anatase -Modification exists. Since it is not known in which form or compounds the cesium is present in the finished catalyst, the content of cesium compounds is calculated as Cs.

Bei der Angabe dieser Zusammensetzung, die die aktiv zur Herstellung der katalytisch aktiven Masse zugesetzten Komponenten umfaßt, wurden gegebenenfalls in den Ausgangs- bzw. Vorläuferverbindungen als technisch unvermeidbare Verunreinigungen enthaltene Elemente nicht berücksichtigt, da diese nicht für jeden Bestandteil und nicht in jedem Versuch analysiert wurden.When specifying this composition, which is actively used to manufacture comprises components added to the catalytically active composition, were optionally in the parent or precursor compounds contained as technically unavoidable impurities Items not taken into account as these are not for each component and were not analyzed in every experiment.

Als inertes, nicht-poröses und unter den Bedingungen der PSA-Herstellung hitzebeständiges Trägermaterial kann der Katalysator gesinterte oder aufgeschmolzene Silikate, z.B. Steatit (Magnesiumsilikat), Porzellan, Tonerde, nicht-poröses Siliciumcarbid, Rutil oder Quarz enthalten, bevorzugt ist das Trägermaterial im erfindungsgemäß eingesetzten Katalysator Steatit. Das Trägermaterial kann zur Beschichtung mit der katalytisch aktiven Masse z.B. in Gestalt von Kugeln, Zylindern, Spiralen oder Ringen eingesetzt werden, vorzugsweise wird ein Träger in Form von Ringen, wie in DE-A 25 10 994 beschrieben, verwendet. Im fertigen Katalysator nimmt die katalytisch aktive Masse, bezogen auf das Gesamtgewicht des Katalysators, im allgemeinen einen Anteil von 8 bis 12 Gew.-%, vorzugsweise von 9 bis 11 Gew.-% und besonders bevorzugt von 9,5 bis 10,5 Gew.-% ein. Unter "fertigen Katalysator" wird in dieser Anmeldung der mit der katalytisch aktiven Masse beschichtete, gegebenenfalls zur Überführung von Vorläuferverbindungen der katalytisch aktiven Komponenten in diese katalytisch aktiven Komponenten und zur Entfernung organischer Hilfsmittel zur Katalysatorherstellung wärmebehandelte, einsatzbereite Katalysator verstanden.As inert, non-porous and under the conditions of PSA production the catalyst can be heat-resistant support material sintered or melted silicates, e.g. steatite (Magnesium silicate), porcelain, clay, non-porous silicon carbide, Contain rutile or quartz, the carrier material is preferred in the catalyst used according to the invention steatite. The Backing material can be coated with the catalytically active Mass e.g. in the form of balls, cylinders, spirals or rings are used, preferably a carrier in the form of rings, as described in DE-A 25 10 994 used. In the finished The catalyst takes the catalytically active mass, based on the Total weight of the catalyst, generally 8 to 12 wt .-%, preferably from 9 to 11 wt .-% and particularly preferably from 9.5 to 10.5% by weight. Under "finished catalyst" is in this application the one with the catalytically active Mass coated, if necessary for the transfer of precursor compounds of the catalytically active components in this catalytically active components and for the removal of organic aids heat-treated, ready-to-use for catalyst production Understood catalyst.

Zur Herstellung des erfindungsgemäß anzuwendenden Katalysators wird Titandioxid in der Anatas-Modifikation verwendet, das im allgemeinen eine BET-Oberfläche von 13 bis 28 m2/g, besonders bevorzugt von 19 bis 21 m2/g und eine Korngröße von im allgemeinen 0,12 bis 1 µ, vorzugsweise von 0,4 bis 0,8 µ hat.To produce the catalyst to be used according to the invention, titanium dioxide is used in the anatase modification, which generally has a BET surface area of 13 to 28 m 2 / g, particularly preferably 19 to 21 m 2 / g and a grain size of generally 0.12 to 1 µ, preferably from 0.4 to 0.8 µ.

Der in der zweiten Reaktionszone erfindungsgemäß zu verwendende Katalysator ist vom Katalysator der ersten Reaktionszone verschieden. Besonders bevorzugt wird in der zweiten Reaktionszone ein Katalysator eingesetzt, der in seiner katalytisch aktiven Masse, bezogen auf das Gesamtgewicht der katalytisch aktiven Masse im fertigen Katalysator, im allgemeinen 1 bis 10 Gew.-%, vorzugsweise 2 bis 9 Gew.-% und besonders bevorzugt 3 bis 8 Gew.-% Vanadiumpentoxid, berechnet als V2O5, im allgemeinen 0 bis 10 Gew.-%, vorzugsweise 0 bis 5 Gew.-% und besonders bevorzugt 0 bis 4 Gew.-% Antimonoxid, berechnet als Sb2O3, im allgemeinen 0,01 bis 0,3 Gew.-%, vorzugsweise 0,05 bis 0,3 Gew.-% und besonders bevorzugt 0,1 bis 0,25 Gew.-% einer Cäsium- und/oder Rubidiumverbindung, berechnet als Cs bzw. Rb, sowie im allgemeinen 0,01 bis Q,3 Gew.-%, vorzugsweise 0,05 bis 0,3 Gew.-% und besonders bevorzugt 0,1 bis 0,25 Gew.-% einer Phosphorverbindung, berechnet als P, enthält. Der Gehalt an einer Phosphorverbindung im Katalysator wird als P berechnet, da nicht bekannt ist, in Form welcher Verbindung oder Verbindungen die bei der Herstellung zugesetzte Phosphorverbindung oder zugesetzten Phosphorverbindungen im fertigen Katalysator vorliegen.The catalyst to be used according to the invention in the second reaction zone is different from the catalyst in the first reaction zone. It is particularly preferred to use a catalyst in the second reaction zone which, in its catalytically active composition, based on the total weight of the catalytically active composition in the finished catalyst, generally 1 to 10% by weight, preferably 2 to 9% by weight and particularly preferably 3 to 8% by weight of vanadium pentoxide, calculated as V 2 O 5 , generally 0 to 10% by weight, preferably 0 to 5% by weight and particularly preferably 0 to 4% by weight of antimony oxide, calculated as Sb 2 O 3 , generally 0.01 to 0.3% by weight, preferably 0.05 to 0.3% by weight and particularly preferably 0.1 to 0.25% by weight of a cesium and / or Rubidium compound, calculated as Cs or Rb, and generally 0.01 to Q.3% by weight, preferably 0.05 to 0.3% by weight and particularly preferably 0.1 to 0.25% by weight a phosphorus compound, calculated as P, contains. The content of a phosphorus compound in the catalyst is calculated as P since it is not known in the form of which compound or compounds the phosphorus compound or phosphorus compounds added in the preparation are present in the finished catalyst.

Selbstverständlich können in der zweiten Reaktionszone auch andere zur Oxidation von aromatischen Kohlenwasserstoffen geeignete Katalysatoren mit einer von der vorstehenden Zusammensetzung verschiedenen Zusammensetzung eingesetzt werden, beispielsweise mit im Handel erhältlichen Katalysatoren oder Katalysatoren wie sie z.B. in DE-A 25 46 268, EP-A 286 448, DE-A 25 47 624, DE-A 29 48 163, EP-A 163 231, DE-A 28 30 765, DE-A 17 69 998, EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 30 45 624 oder DE-A 40 13 051 beschrieben sind.Of course, others can also be used in the second reaction zone suitable for the oxidation of aromatic hydrocarbons Catalysts with a different composition from the above Composition are used, for example with commercially available catalysts or catalysts such as them e.g. in DE-A 25 46 268, EP-A 286 448, DE-A 25 47 624, DE-A 29 48 163, EP-A 163 231, DE-A 28 30 765, DE-A 17 69 998, EP-A 522 871, EP-A 539 878, EP-A 447 267, DE-A 30 45 624 or DE-A 40 13 051 are described.

Die bei den Erläuterungen des in der ersten Reaktionszone erfindungsgemäß vorteilhaft zu verwendenden Katalysators gegebenen Angaben zum Trägermaterial, zur Art des für die katalytisch aktive Masse zu verwendenden Titandioxids und zum Gewichtsanteil der katalytisch aktiven Masse am Gesamtkatalysator, gelten auch für den in der zweiten Reaktionszone erfindungsgemäß vorteilhaft einzusetzenden Katalysator.The explanations of the in the first reaction zone given according to the invention advantageously to be used catalyst Information on the carrier material, the type of for the catalytic active mass of titanium dioxide to be used and the proportion by weight of the catalytically active mass on the overall catalyst also apply advantageous for the invention in the second reaction zone catalyst to be used.

Entsprechend den vorstehenden Angaben zur Zusammensetzung des in der zweiten Reaktionszone vorzugsweise einzusetzenden Katalysators kann dieser Antimon enthalten oder Antimon-frei sein. Das Antimonoxid kann in diesen Katalysatoren z.B. als Sb2O3, Sb2O4 oder Sb2O5 vorliegen, bevorzugt wird Sb2O3 zur Herstellung des Katalysators verwendet.According to the above information on the composition of the catalyst to be used preferably in the second reaction zone, this can contain antimony or be antimony-free. The antimony oxide can be present in these catalysts, for example, as Sb 2 O 3 , Sb 2 O 4 or Sb 2 O 5 , Sb 2 O 3 is preferably used for the preparation of the catalyst.

Die Angaben zur Zusammensetzung des in der zweiten Reaktionszone vorzugsweise verwendeten Katalysators geben die Zusammensetzung der katalytisch aktiven Masse also der Element-Komponenten an, die aktiv zu deren Herstellung eingesetzt wurden. Eventuell in den Ausgangsmaterialien zur Herstellung der katalytisch aktiven Masse enthaltene, technisch unvermeidbare Verunreinigungen wurden bei diesen Angaben nicht berücksichtigt, da diese nicht für jeden Bestandteil und nicht in jedem Versuch analysiert wurden.The information on the composition of the in the second reaction zone preferably used catalyst give the composition the catalytically active mass, i.e. the element components, that were actively used to manufacture them. Possibly in the starting materials for the production of the catalytically active Mass contained, technically unavoidable impurities not taken into account in this information, as this is not for everyone Component and were not analyzed in every trial.

Die Herstellung der in den beiden Reaktionszonen erfindungsgemäß vorteilhaft anzuwendenden Katalysatoren kann auf an sich herkömmliche Weise durch Aufbringen der katalytisch aktiven Masse oder von Vorläuferverbindungen der in der katalytisch aktiven Masse enthaltenen katalytisch aktiven Komponenten auf den Träger erfolgen, beispielsweise wie in DE-A 25 10 994 beschrieben, durch Aufsprühen einer die Komponenten der katalytisch aktiven Masse oder deren Vorläuferverbindungen enthaltenden Maische auf den z.B. auf 100 bis 450°C vorerwärmten Träger, beispielsweise in einer Dragiertrommel. Die katalytisch aktive Masse kann auch anders als durch Aufsprühen, z.B. durch Auftragen einer die katalytisch aktiven Komponenten oder deren Vorläuferverbindungen sowie Hilfsmittel zur Katalysatorherstellung enthaltenden pastösen Masse auf den Träger, z.B. in einer Dragiertrommel, oder durch Auftragen eines die katalytisch aktiven Komponenten und/oder deren Vorläuferverbindungen enthaltenden, z.B. durch Sprüh- oder Gefriertrocknung vorgefertigten Pulvers auf das Trägermaterial, z.B. in einer Dragiertrommel, wobei während des Beschichtungsvorgangs eine geringe Menge eines Lösungsmittel zur Vermittlung der Haftung des Pulvers auf dem vorerwärmten Träger in die Beschichtungsvorrichtung eingesprüht wird, anschließende Trocknung und gegebenenfalls Calcinierung bei Temperaturen bis 450°C, vorzugsweise bis 400°C, auf das Trägermaterial aufgebracht werden. The preparation according to the invention in the two reaction zones Catalysts which can be used advantageously can be conventional per se Way by applying the catalytically active composition or of precursor compounds of the catalytically active mass contained catalytically active components on the carrier, for example as described in DE-A 25 10 994, by spraying one of the components of the catalytically active composition or their mash containing precursor compounds on e.g. preheated to 100 to 450 ° C, for example in a Coating drum. The catalytically active mass can also be different by spraying, e.g. by applying a the catalytically active Components or their precursors and aids for pasty mass containing catalyst preparation the carrier, e.g. in a coating drum, or by application one of the catalytically active components and / or their Containing precursor compounds, e.g. by spray or Freeze drying of prefabricated powder on the carrier material, e.g. in a coating drum, during the coating process a small amount of a solvent to mediate the Adhesion of the powder on the preheated carrier in the coating device is sprayed, subsequent drying and optionally calcination at temperatures up to 450 ° C, preferably up to 400 ° C, are applied to the carrier material.

Zur Herstellung der Maische bzw. der pastösen Masse werden die katalytisch aktiven Komponenten des Katalysators bzw. deren Vorläuferverbindungen beispielsweise in Form ihrer Oxide, Salze, ihrer Nitrate, C1- bis C10-carboxylate, Carbonate, Hydrogencarbonate, Sulfate, Hydrogensulfate, Halogenide oder Phosphate oder als Komplexverbindungen, beispielsweise als Oxalat- oder Acetylaceton-Komplexe sowie gegebenenfalls zur Katalysatorherstellung eingesetzte Hilfsmittel in einem Lösungsmittel gelöst oder, falls diese Stoffe im einzelnen nicht löslich sind, suspendiert. Als Lösungs- oder Suspendierungsmittel können sowohl Wasser als auch organische Flüssigkeiten oder Mischungen des Wassers mit diesen Flüssigkeiten verwendet werden. Vorzugsweise wird Wasser oder Wasser im Gemisch mit organischen Flüssigkeiten verwendet, wobei das Mischungsverhältnis Wasser/organische Flüssigkeit im allgemeinen zwar nicht kritisch ist, vorzugsweise aber solche Lösungsmittelgemische eingesetzt werden, die 50 oder mehr Gewichtsprozent Wasser enthalten.To produce the mash or the pasty mass, the catalytically active components of the catalyst or their precursor compounds are, for example, in the form of their oxides, salts, their nitrates, C 1 - to C 10 -carboxylates, carbonates, bicarbonates, sulfates, hydrogen sulfates, halides or Phosphates or as complex compounds, for example as oxalate or acetylacetone complexes and, if appropriate, auxiliaries used for catalyst preparation are dissolved in a solvent or, if these substances are not individually soluble, suspended. Both water and organic liquids or mixtures of water with these liquids can be used as solvents or suspending agents. Water or water in a mixture with organic liquids is preferably used, the mixing ratio water / organic liquid generally not being critical, but preference being given to using solvent mixtures which contain 50 or more percent by weight of water.

Als organische Flüssigkeiten werden vorzugsweise wasserlösliche Lösungsmittel, wie C1- bis C4-Alkohole, wasserlösliche Ether, z.B. Tetrahydrofuran, Dioxan oder Ethylenglykoldimethylether, wasserlösliche Amide, z.B. Formamid, Pyrrolidon, N-Methylpyrrolidon, N,N-Dimethylformamid oder wasserlösliche Sulfoxide, z.B. Dimethylsulfoxid, verwendet.Organic liquids which are preferably water-soluble solvents, such as C 1 to C 4 alcohols, water-soluble ethers, for example tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, water-soluble amides, for example formamide, pyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide or water-soluble sulfoxides, for example Dimethyl sulfoxide used.

Als Hilfsmittel für die Katalysatorherstellung können der Maische bzw. der pastösen Masse Bindemittel, Porenbildner und/oder temporäre Aktivitätsdämpfungsmittel zugesetzt werden.The mash can be used as an aid for catalyst production or the pasty mass of binders, pore formers and / or temporary Activity dampers are added.

Unter dem Begriff Bindemittel werden hierbei Substanzen verstanden, die die Haftung der einzelnen Partikel der katalytisch aktiven Masse oder deren Vorläuferverbindungen untereinander und/oder auf dem Trägermaterial dauerhaft oder temporär verbessern. Zur Herstellung der erfindungsgemäß zu verwendenden Katalysatoren können als Bindemittel beispielsweise Polyole, wie Ethylenglykol, Propylenglykol, Butylenglykole oder Glycerin oder Amide, wie Formamid, N,N-Dimethylformamid, N,N-Diethylformamid, N,N-Dibutylformamid, Acetamid, Pyrrolidon oder N-Methylpyrrolidon verwendet werden.The term binder here means substances the adhesion of the individual particles of the catalytically active Mass or their precursors to each other and / or Improve permanently or temporarily on the carrier material. to Preparation of the catalysts to be used according to the invention For example, polyols, such as ethylene glycol, Propylene glycol, butylene glycols or glycerin or amides, such as Formamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dibutylformamide, Acetamide, pyrrolidone or N-methylpyrrolidone used become.

Als Porenbildner werden im folgenden Substanzen bezeichnet, die in der Aktivmasse durch eine Volumenänderung, beispielsweise durch Verdampfung oder Zersetzung während der Wärmebehandlung zur Erzeugung der katalytisch aktiven Metalloxide aus deren Vorläuferverbindungen, bei der Herstellung des Schalenkatalysators, die Herausbildung einer im Vergleich zu einer Aktivmasse, bei deren Herstellung kein Porenbildner zugesetzt wurde, geänderte Porenstruktur bewirken. Als Porenbildner können im erfindungsgemäßen Verfahren beispielsweise Polyole, wie Glycerin oder Polymere, wie Cellulose, Methylcellulose, Celluloseacetat oder Stärke, oder Säuren wie Oxalsäure, Weinsäure oder Milchsäure, oder auch Amine, wie Melamin, oder Amide, wie Harnstoff, eingesetzt werden. Die Art und die Menge der zuzusetzenden Hilfsmittel richtet-sich im allgemeinen nach der chemischen Zusammensetzung der katalytisch aktiven Masse des betreffenden Schalenkatalysators und der verwendeten Ausgangsmaterialien und wird zweckmäßigerweise für die jeweils zu erzeugende katalytisch aktive Masse bestimmter chemischer Zusammensetzung in einem Vorversuch optimiert.In the following, substances are referred to as pore formers which in the active mass by a change in volume, for example by evaporation or decomposition during the heat treatment Generation of the catalytically active metal oxides from them Precursor compounds in the manufacture of the coated catalyst, the formation of a compared to an active mass, in the production of which no pore former was added, changed Cause pore structure. As pore formers can Processes according to the invention, for example polyols, such as glycerol or polymers such as cellulose, methyl cellulose, cellulose acetate or starch, or acids such as oxalic acid, tartaric acid or lactic acid, or also amines, such as melamine, or amides, such as urea, be used. The type and amount of tools to be added generally depends on the chemical composition the catalytically active mass of the shell catalyst in question and the raw materials used and will expediently for the catalytically active to be generated in each case Mass of certain chemical composition in a preliminary test optimized.

Unter dem Begriff temporäre Aktivitätsdämpfungsmittel werden oben angegebene Bindemittel oder Porenbildner oder darüber hinaus auch alle weiteren Hilfsstoffe verstanden, die einen begrenzten Zeitraum zu einer Aktivitätsverminderung und/oder zu einer Verringerung der hot spot-Temperatur führen und somit das Anfahren des Reaktors bzw. die Beladungserhöhung bis zu dessen Vollastbetrieb erleichtern ohne die mittlere katalytische Aktivität bzw. Selektivität zu vermindern.The term temporary activity suppressants are used above specified binders or pore formers or beyond understood all other excipients for a limited period of time decrease in activity and / or decrease the hot spot temperature and thus the start of the Reactor or the load increase until its full load operation facilitate without the mean catalytic activity or Reduce selectivity.

Die so hergestellten Katalysatoren werden vorzugsweise zur Gasphasenoxidation von o-Xylol oder Naphthalin oder o-Xylol/Naphthalin-Gemischen zu Phthalsäureanhydrid verwendet.The catalysts thus produced are preferably used for gas phase oxidation of o-xylene or naphthalene or o-xylene / naphthalene mixtures used to phthalic anhydride.

Zu diesem Zweck werden die erfindungsgemäß anzuwendenden Katalysatoren in die Reaktionsrohre gefüllt, die dann vorteilhaft von außen, beispielsweise mittels eines Salzbades, auf die Reaktionstemperatur thermostatisiert werden. Über die so bereitete Katalysatorschüttung wird das Reaktionsgas bei Temperaturen von im allgemeinen 300 bis 450°C, vorzugsweise von 320 bis 420°C und besonders bevorzugt von 340 bis 400°C und bei einem Überdruck von im allgemeinen 0,1 bis 2,5 bar, vorzugsweise von 0,3 bis 1,5 bar mit einer Raumgeschwindigkeit von im allgemeinen 750 bis 5000 h-1 geleitet.For this purpose, the catalysts to be used according to the invention are filled into the reaction tubes, which are then advantageously thermostatted to the reaction temperature from the outside, for example by means of a salt bath. About the catalyst bed prepared in this way, the reaction gas at temperatures of generally 300 to 450 ° C, preferably from 320 to 420 ° C and particularly preferably from 340 to 400 ° C and at an excess pressure of generally 0.1 to 2.5 bar , preferably from 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h -1 passed .

Das dem Katalysator zugeführte Reaktionsgas wird im allgemeinen durch Vermischen von einem molekularen Sauerstoff enthaltenden Gas, vorzugsweise Luft, das außer Sauerstoff noch geeignete Reaktionsmoderatoren und/oder Verdünnungsmittel, wie Dampf, Kohlendioxid und/oder Stickstoff, enthalten kann, mit dem zu oxidierenden, aromatischen Kohlenwasserstoff erzeugt, wobei das molekularen Sauerstoff enthaltende Gas im allgemeinen 1 bis 100 Vol-%, vorzugsweise 2 bis 50 Vol-% und besonders bevorzugt 10 bis 30 Vol-% Sauerstoff, 0 bis 30 Vol-%, vorzugsweise 0 bis 10 Vol-% Wasserdampf sowie 0 bis 50 vol-%, vorzugsweise 0 bis 1 Vol-% Kohlendioxid, Rest Stickstoff, enthalten kann. Zur Erzeugung des Reaktionsgases wird das molekularen Sauerstoff enthaltende Gas im allgemeinen mit 40 g bis 140 g je Nm3 Gas, vorzugsweise mit 60 bis 120 g je Nm3 Gas und besonders bevorzugt mit 80 bis 115 g je Nm3 Gas des zu oxidierenden, aromatischen Kohlenwasserstoffs beschickt.The reaction gas fed to the catalyst is generally obtained by mixing a gas containing molecular oxygen, preferably air, which, in addition to oxygen, may also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized generated, the molecular oxygen-containing gas generally 1 to 100 vol%, preferably 2 to 50 vol% and particularly preferably 10 to 30 vol% oxygen, 0 to 30 vol%, preferably 0 to 10 vol% water vapor and 0 to 50 vol%, preferably 0 to 1 vol% carbon dioxide, the rest nitrogen. To generate the reaction gas, the molecular oxygen-containing gas is generally with 40 g to 140 g per Nm 3 of gas, preferably with 60 to 120 g per Nm 3 of gas and particularly preferably with 80 to 115 g per Nm 3 of the aromatic gas to be oxidized Charged with hydrocarbon.

Vorteilhaft kann die Gasphasenoxidation so durchgeführt werden, daß man zwei oder mehr Zonen, vorzugsweise zwei Zonen der im Reaktionsrohr befindlichen Katalysatorschüttung auf unterschiedliche Reaktionstemperaturen thermostatisiert, wobei beispielsweise Reaktoren mit getrennten Salzbädern, wie sie z.B. in DE-A 22 01 528 oder DE-A 28 30 765 beschrieben sind, eingesetzt werden können. Dabei kann, wie in DE-A 40 13 051 beschrieben, die zum Gaseintritt des Eduktgases hin gelegene Reaktionszone, welche, wie bereits erwähnt, im allgemeinen 25 bis 75 Vol-% des gesamten Katalysatorvolumens umfaßt, auf eine um 1 bis 20°C, vorzugsweise 1 bis 10°C und insbesondere um 2 bis 8°C höhere Reaktionstemperatur als die zum Gasaustritt hin gelegene Reaktionszone thermostatisiert werden. Alternativ kann die Gasphasenoxidation auch ohne Aufteilung in Temperaturzonen in beiden Reaktionszonen bei der gleichen Reaktionstemperatur durchgeführt werden.The gas phase oxidation can advantageously be carried out in such a way that that you have two or more zones, preferably two zones in the reaction tube located catalyst bed on different Reaction temperatures thermostated, for example Reactors with separate salt baths, e.g. in DE-A 22 01 528 or DE-A 28 30 765 are used can be. As described in DE-A 40 13 051, the reaction zone located towards the gas inlet of the reactant gas, which, as already mentioned, generally 25 to 75% by volume of the total Volume of the catalyst, to a temperature of 1 to 20 ° C, preferably 1 to 10 ° C and in particular 2 to 8 ° C higher reaction temperature than the reaction zone towards the gas outlet be thermostatted. Alternatively, the gas phase oxidation even without division into temperature zones in both reaction zones be carried out at the same reaction temperature.

Im allgemeinen wird die Umsetzung durch die Temperatureinstellung des Salzbades so gesteuert, daß in der ersten Zone der größte Teil des im Eduktgas enthaltenen aromatischen Kohlenwasserstoffs bei maximaler Ausbeute umgesetzt wird. Vorzugsweise wird der aromatische Kohlenwasserstoff in der ersten Reaktionszone nahezu vollständig bei maximaler Ausbeute umgesetzt.In general, the reaction is through the temperature setting of the salt bath so that the largest in the first zone Part of the aromatic hydrocarbon contained in the feed gas is implemented at maximum yield. Preferably the aromatic Almost hydrocarbon in the first reaction zone fully implemented at maximum yield.

Mit dem erfindungsgemäßen Verfahren werden, wie durch die nachfolgenden Beispiele belegt, die Nachteile der PSA-Verfahren und Katalysatoren des Standes der Technik auch bei hohen Beladungen des Eduktgasstroms mit o-Xylol und/oder Naphthalin von 80 g/Nm3 Gas und höher vermieden. Dies ist besonders überraschend, da die erfindungsgemäß anzuwendenden Katalysatoren relativ einfach zusammengesetzt sind und der Katalysator der ersten Reaktionszone, verglichen mit anderen Katalysatoren des Standes der Technik, einen sehr niedrigen Vanadiumoxidgehalt hat.As demonstrated by the examples below, the process according to the invention avoids the disadvantages of the PSA processes and catalysts of the prior art, even when the feed gas stream is loaded with o-xylene and / or naphthalene of 80 g / Nm 3 gas and higher. This is particularly surprising since the catalysts to be used according to the invention are of relatively simple composition and the catalyst of the first reaction zone has a very low vanadium oxide content compared to other catalysts of the prior art.

Beispiele:Examples:

In allen Beispielen zur Katalysatorherstellung wurde die BET-Oberfläche nach der Methode von Brunauer et al, J. Am. Chem. Soc. 60, 309 (1938) bestimmt. In all examples for catalyst preparation, the BET surface area was determined by the method of Brunauer et al, J. Am. Chem. Soc. 60 , 309 (1938).

Beispiel 1: Herstellung des Katalysators IExample 1: Preparation of catalyst I.

700 g Steatit-Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel auf 160°C erhitzt und mit einer Suspension aus 400 g Anatas (Analyse: Ti: 59,5 Gew.-%; S: 0,18 Gew.-%; P: 0,08 Gew.-%; Nb: 0,32 Gew.-%; K: 0,007 Gew.-%; Na: 0,04 Gew.-%; Fe: 0,002 Gew.-%; Zr: 0,003 Gew.-%; Pb: 0,003 Gew.-%; W: 0,02 Gew.-%) mit einer BET-Oberfläche von 21 m2/g, 30,7 g Vanadyloxalat, 2,60 g Cäsiumsulfat, 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators entsprach. Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, enthielt 4 Gew.-% Vanadium (berechnet als V2O5), 0,4 Gew.-% Cäsium (berechnet als Cs) und 95,6 Gew.-% Titandioxid.700 g of steatite rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated in a coating drum to 160 ° C. and with a suspension of 400 g of anatase (analysis: Ti: 59, 5% by weight; S: 0.18% by weight; P: 0.08% by weight; Nb: 0.32% by weight; K: 0.007% by weight; Na: 0.04% by weight .-%; Fe: 0.002% by weight; Zr: 0.003% by weight; Pb: 0.003% by weight; W: 0.02% by weight) with a BET surface area of 21 m 2 / g, 30.7 g of vanadyl oxalate, 2.60 g of cesium sulfate, 618 g of water and 128 g of formamide were sprayed until the weight of the layer applied corresponded to 10.5% of the total weight of the finished catalyst. The catalytically active composition applied in this way, ie the catalyst shell, contained 4% by weight of vanadium (calculated as V 2 O 5 ), 0.4% by weight of cesium (calculated as Cs) and 95.6% by weight titanium dioxide.

Beispiel 2: Herstellung des Katalysators IIExample 2: Preparation of catalyst II

700 g Steatit-Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel auf 180°C erhitzt und mit einer Suspension aus 400 g Anatas (Analyse: Ti: 59,5 Gew.-%; S: 0,18 Gew.-%; P: 0,08 Gew.-%; Nb: 0,32 Gew.-%; K: 0,007 Gew.-%; Na: 0,04 Gew.-%; Fe: 0,002 Gew.-%; Zr: 0,003 Gew.-%; Pb: 0,003 Gew.-%; W: 0,02 Gew.-%) mit einer BET-Oberfläche von 21 m2/g, 57,6 g Vanadyloxalat, 14,4 g Antimontrioxid, 2,5 g Ammoniumhydrogenphosphat, 0,65 g Cäsiumsulfat, 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators entsprach. Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, enthielt 0,15 Gew.-% Phosphor (berechnet als P), 7,5 Gew.-% Vanadium (berechnet als V2O5), 3,2 Gew.-% Antimon (berechnet als Sb2O3), 0,1 Gew.-% Cäsium (berechnet als Cs) und 88,75 Gew.-% Titandioxid.700 g steatite rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated in a coating drum to 180 ° C. and with a suspension of 400 g anatase (analysis: Ti: 59, 5% by weight; S: 0.18% by weight; P: 0.08% by weight; Nb: 0.32% by weight; K: 0.007% by weight; Na: 0.04% by weight %; Fe: 0.002% by weight; Zr: 0.003% by weight; Pb: 0.003% by weight; W: 0.02% by weight) with a BET surface area of 21 m 2 / g, 57.6 g of vanadyl oxalate, 14.4 g of antimony trioxide, 2.5 g of ammonium hydrogen phosphate, 0.65 g of cesium sulfate, 618 g of water and 128 g of formamide were sprayed until the weight of the layer applied corresponded to 10.5% of the total weight of the finished catalyst. The catalytically active composition applied in this way, that is to say the catalyst shell, contained 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3.2% by weight. % Antimony (calculated as Sb 2 O 3 ), 0.1% by weight cesium (calculated as Cs) and 88.75% by weight titanium dioxide.

Beispiel 3: Herstellung des Katalysators IIIExample 3: Preparation of catalyst III

700 g Steatit-Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel auf 160°C erhitzt und mit einer Suspension aus 400 g Anatas mit einer BET-Oberfläche von 21 m2/g, 30,7 g Vanadyloxalat, 3,33 g Ammoniumhydrogenphosphat, 2,60 g Cäsiumsulfat, 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators entsprach. Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, enthielt 4,0 Gew.-% Vanadium (berechnet als V2O5), 0,2 Gew.-% Cäsium (berechnet als Cs), 0,2 Gew.-% Phosphor (berechnet als P) und 95,4 Gew.-% Titandioxid.700 g steatite rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated in a coating drum to 160 ° C and with a suspension of 400 g anatase with a BET surface area of 21 m 2 / g, 30.7 g of vanadyl oxalate, 3.33 g of ammonium hydrogen phosphate, 2.60 g of cesium sulfate, 618 g of water and 128 g of formamide were sprayed until the weight of the layer applied corresponded to 10.5% of the total weight of the finished catalyst. The catalytically active composition applied in this way, that is to say the catalyst shell, contained 4.0% by weight of vanadium (calculated as V 2 O 5 ), 0.2% by weight of cesium (calculated as Cs), 0.2% by weight. % Phosphorus (calculated as P) and 95.4% by weight titanium dioxide.

Beispiel 4: Katalysatorsystem AExample 4: Catalyst System A

Es wurde in der-ersten Reaktionszone Katalysator I und in der zweiten Reaktionszone Katalysator II eingesetzt, deren katalytisch aktive Masse folgende Zusammensetzung in Gew.-%, bezogen auf das Gewicht der katalytisch aktiven Masse im fertigen Katalysator, hatte: Katalysator I Katalysator II V2O5 4,0 7,5 Sb2O3 - 3,2 Cs 0,4 0,1 Phosphor (P) - 0,15 Rest Anatas Anatas Catalyst I was used in the first reaction zone and catalyst II in the second reaction zone, the catalytically active composition of which had the following composition in% by weight, based on the weight of the catalytically active composition in the finished catalyst: Catalyst I Catalyst II V 2 O 5 4.0 7.5 Sb 2 O 3 - 3.2 Cs 0.4 0.1 Phosphorus (P) - 0.15 rest anatase anatase

Ein Reaktionsrohr aus Stahl, von 3,5 m Länge und 25 mm Innendurchmesser, wurde im unteren Teil mit Katalysator II und im darüberliegenden Teil mit Katalysator I gefüllt. Die Füllhöhe des Katalysators II betrug 130 cm, die des Katalysators I 160 cm. Im oberen Teil war das Reaktionsrohr am Gaseingang in einer Länge von 50 cm frei von Katalysator. Das Reaktionsrohr wurde mit einem flüssigen Wärmeträgermedium (Salzbad) thermostatisiert, über das auch die Reaktionswärme abgeführt wurde.A reaction tube made of steel, 3.5 m long and 25 mm inside diameter, was in the lower part with catalyst II and in part overlying filled with catalyst I. The fill level of the Catalyst II was 130 cm, that of Catalyst I 160 cm. in the The upper part was the reaction tube at the gas inlet in one length of 50 cm free of catalyst. The reaction tube was equipped with a liquid heat transfer medium (salt bath) thermostatted the heat of reaction was also removed.

Der Katalysatorträger bestand aus zylindrischen Ringen in den Abmessungen 6 mm (Höhe), 8 mm (Breite) und 5 mm (lichte Weite).The catalyst carrier consisted of cylindrical rings in dimensions 6 mm (height), 8 mm (width) and 5 mm (clear width).

Das Reaktionsrohr wurde mit stündlich 4 m3 Luft von oben nach unten durchströmt, wobei die o-Xylol-Beladung 95 g/m3 Luft betrug. Die Reinheit des o-Xylols war 98,2 %ig. Bei einer Salzbadtemperatur von 350°C erreichte die hot spot-Temperatur im Katalysatorbett 430 bis 440°C. Der hot spot befand sich in ca. 40 bis 60 cm Tiefe der ersten Reaktionszone.The reaction tube was flowed through with 4 m 3 of air per hour from top to bottom, the o-xylene loading being 95 g / m 3 of air. The purity of the o-xylene was 98.2%. At a salt bath temperature of 350 ° C, the hot spot temperature in the catalyst bed reached 430 to 440 ° C. The hot spot was about 40 to 60 cm deep in the first reaction zone.

Das aus dem Reaktionsrohr austretende Reaktionsgas bestand in seinen organischen Bestandteilen zu 95,8 Gew.-% aus Phthalsäureanhydrid. Wesentliche Nebenprodukte waren Maleinsäureanhydrid (3,2 Gew.-%), Benzoesäure (0,51 Gew.-%), Phthalid (0,07 Gew.-%) und Citraconsäureanhydrid (0,34 Gew.-%). The reaction gas emerging from the reaction tube consisted of its organic components to 95.8 wt .-% from phthalic anhydride. The main by-products were maleic anhydride (3.2% by weight), benzoic acid (0.51% by weight), phthalide (0.07% by weight) and citraconic anhydride (0.34% by weight).

Die gebildete PSA-Menge betrug 435 g/h, entsprechend einer PSA-Ausbeute von 83,5 mol-% bezogen auf 100 %iges o-Xylol. Das aus dem Reaktionsgas abgeschiedene Roh-PSA ließ sich in einer 2-stufigen Vakuumdestillation problemlos und ohne Vorbehandlung zu Rein-PSA der GC-Reinheit 99,9 % aufarbeiten. Die Schmelzfarbzahl betrug 5 bis 10 (APHA), die Hitzefarbzahl (90 Min. bei 250°C) 10 bis 20 (APHA).The amount of PSA formed was 435 g / h, corresponding to a PSA yield of 83.5 mol% based on 100% o-xylene. The end crude PSA separated from the reaction gas could be in a 2-stage Vacuum distillation without problems and without pretreatment Process pure PSA of GC purity 99.9%. The melt color number was 5 to 10 (APHA), the heat color number (90 min at 250 ° C) 10 to 20 (APHA).

Nach einjähriger Betriebszeit des Katalysators betrug die PSA-Ausbeute noch 82,7 mol-%.After one year of operating the catalyst, the PSA yield was still 82.7 mol%.

Die für den Umweltschutz kritischen Stoffe o-Xylol bzw. Benzol waren im Reaktionsgas mit 31 mg/m3 bzw. 2,5 mg/m3 enthalten. Aufgrund ihrer geringen Konzentrationen brauchten diese Stoffe aus dem Abgas nicht entfernt bzw. abgereichert werden.The substances o-xylene and benzene, which are critical for environmental protection, were contained in the reaction gas at 31 mg / m 3 and 2.5 mg / m 3, respectively. Because of their low concentrations, these substances did not need to be removed or depleted from the exhaust gas.

Beispiel 5: Katalysatorsystem BExample 5: Catalyst system B

Es wurde in der ersten Reaktionszone Katalysator I und in der zweiten Reaktionszone Katalysator III eingesetzt, deren katalytisch aktive Masse folgende Zusammensetzung in Gew.-%, bezogen auf das Gewicht der katalytisch aktiven Masse im fertigen Katalysator, hatte: Katalysator I Katalysator III V2O5 4,0 4,0 Cs 0,4 0,2 Phosphor (P) - 0,2 Rest Anatas Anatas Catalyst I was used in the first reaction zone and catalyst III in the second reaction zone, the catalytically active composition of which had the following composition in% by weight, based on the weight of the catalytically active composition in the finished catalyst: Catalyst I Catalyst III V 2 O 5 4.0 4.0 Cs 0.4 0.2 Phosphorus (P) - 0.2 rest anatase anatase

Ein Reaktionsrohr aus Stahl, von 3,5 m Länge und 25 mm Innendurchmesser, wurde im unteren Teil mit Katalysator III und im darüberliegenden Teil mit Katalysator I gefüllt. Die Füllhöhe des Katalysators III betrug 130 cm, die des Katalysators I 170 cm.
Der obere Teil des Reaktionsrohres war am Gaseintritt in einer Länge von 40 cm leer.A reaction tube made of steel, 3.5 m long and 25 mm inside diameter, was filled with catalyst III in the lower part and with catalyst I in the part above. The filling height of the catalyst III was 130 cm, that of the catalyst I 170 cm.
The upper part of the reaction tube was empty at a length of 40 cm at the gas inlet.

Das Reaktionsrohr wurde mit einem flüssigen Wärmeträgermedium (Salzbad) thermostatisiert, über das auch die Reaktionswärme abgeführt wurde.The reaction tube was filled with a liquid heat transfer medium (Salt bath) thermostatted, via which the heat of reaction is also dissipated has been.

Der Katalysatorträger bestand aus zylindrischen Ringen in den Abmessungen 6,5 mm (Höhe), 7 mm (Breite) und 4 mm (lichte Weite). The catalyst carrier consisted of cylindrical rings in dimensions 6.5 mm (height), 7 mm (width) and 4 mm (clear width).

Das Reaktionsrohr aus Beispiel 1 wurde mit stündlich 4 m3 Luft von oben nach unten durchströmt. Die o-Xylol-Beladung der Luft betrug dabei 85 g/m3. Die Reinheit des o-Xylols war 98,2 %. Bei einer Salzbadtemperatur von 355°C erreichte die hot spot-Temperatur 435 bis 445°C. Der hot spot befand sich in ca. 60 bis 70 cm Tiefe der ersten Reaktionszone.The reaction tube from Example 1 was flowed through with 4 m 3 of air per hour from top to bottom. The o-xylene loading in the air was 85 g / m 3 . The purity of the o-xylene was 98.2%. At a salt bath temperature of 355 ° C, the hot spot temperature reached 435 to 445 ° C. The hot spot was about 60 to 70 cm deep in the first reaction zone.

Das aus dem Reaktionsrohr austretende Reaktionsgas bestand in seinen organischen Bestandteilen zu 95,9 Gew.-% aus Phthalsäureanhydrid. Wesentliche Nebenprodukte waren Maleinsäureanhydrid (2,87 Gew.-%), Benzoesäure (0,49 Gew.-%), Phthalid (0,18 Gew.%) und Citraconsäureanhydrid (0,35 Gew.-%).The reaction gas emerging from the reaction tube consisted of its organic components to 95.9 wt .-% from phthalic anhydride. The main by-products were maleic anhydride (2.87% by weight), benzoic acid (0.49% by weight), phthalide (0.18% by weight) and citraconic anhydride (0.35% by weight).

Es wurden stündlich 388 g PSA gebildet, entsprechend einer PSA-Ausbeute von 83,2 mol-%, bezogen auf 100 %iges o-Xylol. Das aus dem Reaktionsgas gewonnene Roh-PSA ließ sich in einer 2-stufigen Vakuumdestillation problemlos und ohne Vorbehandlung zu Rein-PSA mit einer GC-Reinheit von 99,9 % aufarbeiten. Die Schmelzfarbzahl des Rein-Produktes betrug 5 bis 10 (APHA), die Hitzefarbzahl (90 Min. bei 250°C) 20 (APHA).388 g of PSA were formed per hour, corresponding to a PSA yield of 83.2 mol%, based on 100% o-xylene. The end The raw PSA obtained from the reaction gas could be divided into two stages Vacuum distillation easily and without pretreatment to pure PSA Work up with a GC purity of 99.9%. The melt color number the pure product was 5 to 10 (APHA), the heat color number (90 min at 250 ° C) 20 (APHA).

Nach 10-monatiger Betriebszeit des Katalysators betrug die PSA-Ausbeute noch 82,8 mol-%.After 10 months of catalyst operation, the PSA yield was still 82.8 mol%.

Die für den Umweltschutz problematischen Stoffe o-Xylol und Benzol lagen in vergleichbaren Konzentrationen wie in Beispiel 1 beschrieben vor. Eine Abreicherung aus dem Abgas war auch hier nicht erforderlich.The substances that are problematic for environmental protection are o-xylene and The concentrations of benzene were comparable to those in Example 1 described before. A depletion from the exhaust gas was also here not mandatory.

Claims (3)

  1. A process for preparing phthalic anhydride by catalytic gas-phase oxidation of o-xylene or naphthalene or o-xylene/naphthalene mixtures with a gas comprising molecular oxygen over a coated catalyst comprising an inert, nonporous support material on which a catalytically active composition comprising titanium dioxide and vanadium pentoxide is applied in layer form, wherein a catalyst whose catalytically active composition comprises from 3 to 6% by weight of vanadium pentoxide, calculated as V2O5, from 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder to 100% by weight of titanium dioxide in the anatase modification is used in the presence or absence of a coated catalyst, differing therefrom, for the catalytic gas-phase oxidation of o-xylene or naphthalene or o-xylene/naphthalene mixtures and, in the presence of such a second catalyst, the latter is used in a combined bed with the catalyst of the above composition in the reactor.
  2. A process as claimed in claim 1, wherein the coated catalyst used in a first reaction zone nearest the gas inlet into the reactor is one whose catalytically active composition comprises from 3 to 6% by weight of vanadium pentoxide, calculated as V2O5, from 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder to 100% by weight of titanium dioxide in the anatase modification and the coated catalyst used in a second reaction zone nearest the outlet for the reaction gases from the reactor is one whose catalytically active composition comprises from 1 to 10% by weight of vanadium pentoxide, calculated as V2O5, from 0 to 10% by weight of antimony oxide, calculated as Sb2O3, from 0.01 to 0.3% by weight of a cesium and/or rubidium compound, calculated as Cs or Rb, from 0.01 to 0.3% by weight of a phosphorus compound, calculated as P, and the remainder to 100% by weight of titanium dioxide in the anatase modification.
  3. A catalyst comprising a thin layer of catalytically active components applied in the form of a shell to a nonporous support material, wherein the catalytically active composition comprises from 3 to 6% by weight of vanadium pentoxide, calculated as V2O5, from 0.3 to 0.5% by weight of a cesium compound, calculated as Cs, and the remainder to 100% by weight of titanium dioxide in the anatase modification.
EP98912298A 1997-02-27 1998-02-12 Method for producing phthalic anhydride; shell catalyst containing titanium-vanadium-cesium Expired - Lifetime EP0964744B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19707943 1997-02-27
DE19707943A DE19707943C2 (en) 1997-02-27 1997-02-27 Process for the preparation of phthalic anhydride and catalyst therefor
PCT/EP1998/000779 WO1998037965A1 (en) 1997-02-27 1998-02-12 Method for producing acid phthalic anhydride and an appropriate shell catalyst containing titanium-vanadium-cesium

Publications (2)

Publication Number Publication Date
EP0964744A1 EP0964744A1 (en) 1999-12-22
EP0964744B1 true EP0964744B1 (en) 2003-04-23

Family

ID=7821709

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98912298A Expired - Lifetime EP0964744B1 (en) 1997-02-27 1998-02-12 Method for producing phthalic anhydride; shell catalyst containing titanium-vanadium-cesium

Country Status (11)

Country Link
US (1) US6458970B1 (en)
EP (1) EP0964744B1 (en)
JP (1) JP2001513091A (en)
KR (1) KR100450357B1 (en)
CN (1) CN1104279C (en)
AT (1) ATE238099T1 (en)
DE (2) DE19707943C2 (en)
ES (1) ES2198051T3 (en)
MY (1) MY120022A (en)
TW (1) TW425393B (en)
WO (1) WO1998037965A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011032658A1 (en) 2009-09-17 2011-03-24 Süd-Chemie AG Method for producing a catalyst arrangement for preparing phthalic anhydride
DE102009049173A1 (en) 2009-10-13 2011-04-21 Süd-Chemie AG Reactor arrangement for catalytic gas phase oxidation
DE102010006854A1 (en) 2010-02-04 2011-08-04 Süd-Chemie AG, 80333 Process for the gas phase oxidation of hydrocarbons
WO2011113920A1 (en) 2010-03-19 2011-09-22 Süd-Chemie AG Method for the catalytic gas phase oxidation of hydrocarbons and catalysis reaction device

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1011577A3 (en) * 1997-11-27 1999-11-09 Solvay Epoxidation catalyst, use and method epoxidation catalyst presence.
DE19823275A1 (en) 1998-05-26 1999-12-02 Basf Ag Process for the preparation of phthalic anhydride by catalytic gas phase oxidation of x-xylene - / - naphthalene mixtures
DE19823262A1 (en) 1998-05-26 1999-12-02 Basf Ag Process for the preparation of phthalic anhydride
DE19839001A1 (en) 1998-08-27 2000-03-02 Basf Ag Shell catalysts for the catalytic gas phase oxidation of aromatic hydrocarbons
DE19939629A1 (en) * 1999-08-20 2001-02-22 Basf Ag Production of pure phthalic anhydride, e.g. for plasticizer production, involves distillation under reduced pressure in a column from which volatiles are taken off at the top and pure anhydride is taken off at a side arm
DE10206989A1 (en) 2002-02-19 2003-08-21 Basf Ag Production of phthalic anhydride involves gas-phase oxidation of o-xylene or naphthalene in a tubular reactor containing three or more different catalyst beds with controlled hot-spot temperatures
DE10323817A1 (en) * 2003-05-23 2004-12-09 Basf Ag Process for the preparation of phthalic anhydride
DE10323818A1 (en) * 2003-05-23 2004-12-09 Basf Ag Catalyst systems for the production of phthalic anhydride
CN100429209C (en) * 2003-08-14 2008-10-29 中国石油化工股份有限公司 Method for preparing phthalic anhydride
DE102004026472A1 (en) * 2004-05-29 2005-12-22 Süd-Chemie AG Multi-layer catalyst for the production of phthalic anhydride
CN100496740C (en) * 2004-05-29 2009-06-10 苏德-化学股份公司 Multi-layer catalyst for producing phthalic anhydride
US8097558B2 (en) * 2004-05-29 2012-01-17 Sud-Chemie Ag Catalyst and method for producing phthalic anhydride
CN101060927B (en) * 2004-11-18 2011-05-11 巴斯福股份公司 Use of titanium dioxide mixtures for producing catalysts
TWI376266B (en) * 2005-03-02 2012-11-11 Sued Chemie Ag Process for manufacture of a multiple layer catalyst for producing phthalic acid anhydride
DE102005009473A1 (en) * 2005-03-02 2006-09-07 Süd-Chemie AG Multi-layer catalyst for the production of phthalic anhydride
KR100939142B1 (en) * 2005-05-22 2010-01-28 쉬드-케미아크티엔게젤샤프트 Multi-layered catalyst for producing phthalic anhydride
EP1860091A1 (en) * 2006-05-23 2007-11-28 Süd-Chemie Ag Catalyst containing titanium dioxide, particularly for the production of phthalic anhydride
CN101130535B (en) * 2006-08-25 2010-10-13 中国石油化工股份有限公司 Method for producing phthallic anhydride
DE102008011011A1 (en) * 2008-02-01 2009-08-06 Breimair, Josef, Dr. Catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides, in particular to phthalic anhydride
JP5386096B2 (en) * 2008-02-27 2014-01-15 三菱重工業株式会社 Exhaust gas treatment catalyst
MY193099A (en) * 2016-07-26 2022-09-26 Basf Corp Supported catalyst, monolithic selective catalytic reduction (scr) catalyst, preparation method therefor, and method for nitrogen oxides removal
CN112912174A (en) * 2018-09-05 2021-06-04 沙特基础全球技术有限公司 Vanadium oxide supported catalysts for alkane dehydrogenation
CN109395778B (en) * 2018-11-13 2021-10-22 北京林业大学 Niobium phytate supported nano metal catalytic system for levulinic acid and ester hydrogenation
CN112536053B (en) * 2019-09-23 2023-09-08 中国石油化工股份有限公司 Catalyst for preparing phthalic anhydride from o-xylene and preparation method thereof

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1769998B2 (en) 1968-08-20 1977-01-27 Basf Ag, 6700 Ludwigshafen PROCESS FOR MANUFACTURING PHTHALIC ANHYDRIDE
BE793928A (en) 1972-01-13 1973-05-02 Deggendorfer Werft Eisenbau APPARATUS FOR IMPLEMENTING EXOTHERMAL AND ENDOTHERMAL CHEMICAL PROCESSES
DE2260615A1 (en) 1972-12-12 1974-06-20 Basf Ag SUPPORT CATALYST FOR THE OXIDATION OF O-XYLOL OR NAPHTHALINE TO PHTHALIC ANHYDRIDE
DE2436009C3 (en) 1974-07-26 1982-04-22 Basf Ag, 6700 Ludwigshafen Process for the production of phthalic anhydride
JPS5143732A (en) 1974-10-11 1976-04-14 Nippon Catalytic Chem Ind Musuifutarusanno seizohoho
DE2510994B2 (en) 1975-03-13 1977-04-14 Basf Ag, 6700 Ludwigshafen SUPPORT CATALYST CONTAINING VANADIUM AND TITANIUM
DE2546268C3 (en) 1975-10-16 1983-11-24 Basf Ag, 6700 Ludwigshafen Process for the production of phthalic anhydride from o-xylene or naphthalene
DE2547624C2 (en) 1975-10-24 1981-10-08 Basf Ag, 6700 Ludwigshafen Supported catalysts containing vanadium pentoxide, titanium dioxide, antimony and rubidium
AU529228B2 (en) 1977-07-13 1983-06-02 Nippon Shokubai Kagaku Kogyo Co. Ltd. Catalytic vapour phase oxidation
JPS603307B2 (en) 1978-11-29 1985-01-26 株式会社日本触媒 Method for producing phthalic anhydride
DE2925682A1 (en) 1979-06-26 1981-01-29 Basf Ag VANADINE PENTOXIDE, TITANIUM DIOXIDE, PHOSPHORUS, RUBIDIUM AND / OR CAESIUM AND Possibly. ZIRCONDIOXIDE CONTAINING CARRIER CATALYST
JPS591378B2 (en) 1979-12-03 1984-01-11 株式会社日本触媒 Catalyst for phthalic anhydride production
DE3760124D1 (en) 1986-10-07 1989-06-01 Freudenberg Carl Fa Shaft coupling
JPS63253080A (en) 1987-04-10 1988-10-20 Nippon Steel Chem Co Ltd Production of phthalic anhydride
US5169820A (en) * 1990-03-16 1992-12-08 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalyst for producing phthalic anhydride
US5235071A (en) * 1991-07-10 1993-08-10 Nippon Shokubai Co., Ltd. Catalyst for producing phthalic anhydride and process by using the same
DE69207552T2 (en) 1991-10-25 1996-06-05 Nippon Catalytic Chem Ind Process for the preparation of phthalic anhydride by oxidation of the mixture of ortho-xylene with naphthalene
DE19519172A1 (en) * 1995-05-24 1996-11-28 Consortium Elektrochem Ind Supported catalyst for gas phase oxidation reactors

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011032658A1 (en) 2009-09-17 2011-03-24 Süd-Chemie AG Method for producing a catalyst arrangement for preparing phthalic anhydride
DE102009041960A1 (en) 2009-09-17 2011-04-07 Süd-Chemie AG Process for preparing a catalyst arrangement for the production of phthalic anhydride
US8796173B2 (en) 2009-09-17 2014-08-05 Süd-Chemie Ip Gmbh & Co. Kg Method for producing a catalyst arrangement for the production of phthalic anhydride
DE102009049173A1 (en) 2009-10-13 2011-04-21 Süd-Chemie AG Reactor arrangement for catalytic gas phase oxidation
WO2011045051A1 (en) 2009-10-13 2011-04-21 Süd-Chemie AG Reactor array for catalytic gas phase oxidation
DE102010006854A1 (en) 2010-02-04 2011-08-04 Süd-Chemie AG, 80333 Process for the gas phase oxidation of hydrocarbons
WO2011095416A1 (en) 2010-02-04 2011-08-11 Süd-Chemie AG Method for gas phase oxidation of hydrocarbons
WO2011113920A1 (en) 2010-03-19 2011-09-22 Süd-Chemie AG Method for the catalytic gas phase oxidation of hydrocarbons and catalysis reaction device
DE102010012090A1 (en) 2010-03-19 2011-11-17 Süd-Chemie AG Process for the catalytic gas phase oxidation of hydrocarbons and catalytic reaction apparatus

Also Published As

Publication number Publication date
DE19707943A1 (en) 1998-09-03
CN1104279C (en) 2003-04-02
KR100450357B1 (en) 2004-10-01
TW425393B (en) 2001-03-11
JP2001513091A (en) 2001-08-28
EP0964744A1 (en) 1999-12-22
CN1248929A (en) 2000-03-29
MY120022A (en) 2005-08-30
ES2198051T3 (en) 2004-01-16
US6458970B1 (en) 2002-10-01
KR20000075728A (en) 2000-12-26
DE19707943C2 (en) 1999-07-08
WO1998037965A1 (en) 1998-09-03
DE59808067D1 (en) 2003-05-28
ATE238099T1 (en) 2003-05-15

Similar Documents

Publication Publication Date Title
EP0964744B1 (en) Method for producing phthalic anhydride; shell catalyst containing titanium-vanadium-cesium
EP0966324B1 (en) Method for producing shell catalysts for catalytic gas-phase oxidation of aromatic hydrocarbons
DE3884441T2 (en) Process for the preparation of phthalic anhydride.
EP1082317B1 (en) Method for producing phthalic anhydride by means of catalytic vapor-phase oxidation of o-xylol/naphthalene mixtures
EP1117484B1 (en) Multilayered shell catalysts for catalytic gaseous phase oxidation of aromatic hydrocarbons
DE69016590T2 (en) Process for the production of acrylic acid.
EP0744214B1 (en) Supported catalyst for oxidation reactions in the gas phase
EP1159246B1 (en) Method for the catalytic gas phase oxidation of acrolein into acrylic acid
EP0015565B1 (en) Process for the production of alpha,beta olefinically unsaturated aldehydes containing 3 or 4 c-atoms
EP1735093B1 (en) Catalyst having a silver-vanadium oxide phase and a promoter phase
EP0951351B1 (en) Use of a shell catalyst for producing acetic acid by gas phase oxidation of unsaturated c 4 hydrocarbons
DE102008044890B4 (en) Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and/or carboxylic anhydrides, in particular to phthalic anhydride, and process for producing such a catalyst
DE2526238A1 (en) PROCESS FOR THE PRODUCTION OF ACRYLIC ACID OR METHACRYLIC ACID BY OXYDATION OF ACROLEIN OR METHACROLEIN
DE2626887A1 (en) CATALYST FOR THE OXIDATION OF (METH) ACROLEIN TO (METH) ACRYLIC ACID
DE2025430C3 (en) Coated catalysts
EP1860091A1 (en) Catalyst containing titanium dioxide, particularly for the production of phthalic anhydride
EP1654211B1 (en) Multi-metal oxide containing silver, vanadium and a promoter metal and use thereof
DE3410799C2 (en)
EP0960874B1 (en) Method of production of acetic acid by gas phase oxidation of saturated C4-hydrocarbons and their mixtures with unsaturated C4-hydrocarbons
DE2430567A1 (en) PROCESS FOR PRODUCING ANTHRAQUINONE
DE2632395C3 (en) Catalyst for use in the manufacture of anisaldehyde
DE2321799A1 (en) CATALYST MIXTURE FOR OXIDATING O-XYLOL OR NAPHTHALINE TO PHTHALIC ANHYDRIDE
DE2658861A1 (en) METHOD FOR PRODUCING MALEIC ACID ANHYDRIDE
DE3543822A1 (en) METHOD FOR THE CATALYTIC OXIDATION OF 4-TERTIA BUTYL-O-XYLOL
EP1888229B1 (en) Multi-layered catalyst for producing phthalic anhydride

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990810

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RTI1 Title (correction)

Free format text: METHOD FOR PRODUCING PHTHALIC ANHYDRIDE; SHELL CATALYST CONTAINING TITANIUM-VANADIUM-CESIUM

17Q First examination report despatched

Effective date: 20020322

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE DE ES FR GB IT NL SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59808067

Country of ref document: DE

Date of ref document: 20030528

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2198051

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040126

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050209

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060212

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060212

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20070204

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20070206

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20070213

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070327

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070522

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070208

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20080415

Year of fee payment: 11

EUG Se: european patent has lapsed
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080901

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080212

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080229

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080213

BERE Be: lapsed

Owner name: *BASF A.G.

Effective date: 20090228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130429

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59808067

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59808067

Country of ref document: DE

Effective date: 20140902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140902